WO2009136631A1 - 新規スルホン酸基含有セグメント化ブロック共重合体ポリマー及びその用途、新規ブロック共重合体ポリマーの製造方法 - Google Patents
新規スルホン酸基含有セグメント化ブロック共重合体ポリマー及びその用途、新規ブロック共重合体ポリマーの製造方法 Download PDFInfo
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- WO2009136631A1 WO2009136631A1 PCT/JP2009/058665 JP2009058665W WO2009136631A1 WO 2009136631 A1 WO2009136631 A1 WO 2009136631A1 JP 2009058665 W JP2009058665 W JP 2009058665W WO 2009136631 A1 WO2009136631 A1 WO 2009136631A1
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- Prior art keywords
- block copolymer
- group
- polymer
- oligomer
- exchange membrane
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- 229910052736 halogen Inorganic materials 0.000 claims description 20
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- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical group FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001308 synthesis method Methods 0.000 claims description 14
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- WWQLXRAKBJVNCC-UHFFFAOYSA-N bis(2,3,4,5,6-pentafluorophenyl)methanone Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1C(=O)C1=C(F)C(F)=C(F)C(F)=C1F WWQLXRAKBJVNCC-UHFFFAOYSA-N 0.000 claims description 5
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Classifications
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Definitions
- the present invention relates to a sulfonic acid group-containing segmented block copolymer having a novel structure, its use and a method for synthesizing a sulfonic acid group-containing segmented block copolymer having a novel structure. Furthermore, the present invention relates to a composition, a molded product, a proton exchange membrane for a fuel cell, and a fuel cell containing the polymer as a constituent component.
- Solid polymer fuel cells PEFCs
- DMFCs direct methanol fuel cells
- proton exchange membrane a perfluorocarbon sulfonic acid polymer membrane represented by Nafion (registered trademark) manufactured by DuPont of the United States is widely used.
- a proton exchange membrane with higher heat resistance is required.
- a heat-resistant proton exchange membrane a sulfonated polymer obtained by treating a heat-resistant polymer such as polysulfone or polyetherketone with a sulfonating agent such as fuming sulfuric acid is well known (for example, see Non-Patent Document 1).
- a sulfonated polymer obtained by treating a heat-resistant polymer such as polysulfone or polyetherketone with a sulfonating agent such as fuming sulfuric acid is well known (for example, see Non-Patent Document 1).
- Patent Document 1 As a proton conductive polymer, 4,4′-dichlorodiphenylsulfone-3,3′-sodium disulfonate, and 4,4′-biphenol are reacted with 4,4′-dichlorodiphenylsulfone. The resulting copolymer is shown.
- the proton exchange membrane containing this polymer as a constituent component has less sulfonic acid group heterogeneity as in the case of using the sulfonating agent described above, and the amount of sulfonic acid group introduced and the molecular weight of the polymer can be easily controlled. However, improvement of various characteristics such as proton conductivity is desired for practical use as a fuel cell.
- Patent Document 2 describes a sulfonated polyethersulfone segmented block copolymer.
- One method of obtaining this polymer is sulfonation of a block polymer composed of segments that are easily and easily sulfonated.
- this method has a disadvantage that the sulfonation reaction is locally performed due to the difference in electron density of the benzene ring in each segment, and the polymer structure of each segment is limited.
- a benzene ring to which an oxygen atom of an ether group or an electron donating group such as an alkyl group is bonded is easily sulfonated, but a reverse reaction due to heat, hydrolysis, or the like easily occurs. Therefore, the above polymer also has a problem that the stability of the sulfonic acid group in the polymer is low.
- a separation membrane is mentioned as an application of this polymer, it has not been described as to the use as a proton exchange membrane for a fuel cell.
- Patent Document 3 describes that a polymer obtained by sulfonation of a segmented block copolymer having a specific repeating unit is used as a proton exchange membrane of a fuel cell.
- this polymer also utilizes the difference in reactivity to sulfonation as in the polymer of Patent Document 2, the structure of the hydrophobic segment has been limited.
- Examples of other sulfonated segmented block copolymer include the polymers described in Patent Document 4.
- the polymer of Patent Document 4 is characterized in that the arrangement of the main chain at the block transition part is the same as the inside of the block, but the polymer structure has also been limited.
- Patent Document 5 also describes a proton exchange membrane for a fuel cell using a sulfonated polyethersulfone segmented block copolymer.
- Patent Document 6 or 7 discloses a sulfonated polyethersulfone segmented block copolymer containing a halogen in a repeating unit as a polymer used in a proton exchange membrane for a fuel cell.
- some of these polymers have high swellability, and there are cases where there is a problem in durability when used in a fuel cell.
- many monomers containing a halogen element are difficult to synthesize or expensive, and there is a problem that there are many difficulties in polymer synthesis.
- the polymer contains a large amount of halogen elements, there are problems in disposal such as generation of harmful gases when incinerated.
- Non-patent Document 8 As a polymer used for a proton exchange membrane for a fuel cell, a sulfonated polyethersulfone segmented block copolymer having a structure having a halogen element such as fluorine at the end of a specific segment is disclosed in Patent Document 8 or Non-patent Document 2.
- block copolymerization in which both end oligomers are reacted using an aromatic chain extender containing a halogen element such as fluorine, with the same end group of each segment. The synthesis of the polymer is reported in Non-Patent Document 3.
- the main problem of the present invention is not only a proton exchange membrane obtained from an existing polymer, but also a fuel that is superior in proton conductivity and less in swelling with hot water and excellent in durability.
- PROTON EXCHANGE MEMBRANE FOR BATTERY, SULFONIC ACID-CONTAINING SEGMENTED BLOCK COPOLYMER COMPRISING THE PROTON EXCHANGE MEMBRANE, MANUFACTURING METHOD OF THE POLYMER, COMPOSITION AND MOLDED ARTICLE OF THE POLYMER, PROTON EXCHANGE MEMBRANE ELECTRODE FOR FUEL CELL Provided is a joined body and a fuel cell.
- the first invention of the present application is (1) A block copolymer having at least one hydrophilic segment and hydrophobic segment in the molecule, and having a structure represented by the following chemical formula 1, using N-methyl-2-pyrrolidone as a solvent A block copolymer having a logarithmic viscosity measured at 30 ° C. of a 0.5 g / dL solution in the range of 0.5 to 5.0 dL / g.
- X is H or a monovalent cation
- Y is a sulfone group or a carbonyl group
- Z and Z ′ are each independently an O or S atom
- W is a direct bond between benzenes.
- Ar 1 and Ar 2 are each independently a divalent aromatic group
- n and m are each independently 2 to 100 Each represents an integer.
- the second invention of the present application is (13) In a method of synthesizing a block copolymer polymer by reacting a hydrophilic oligomer, a hydrophobic oligomer and a chain extender,
- the hydrophobic oligomer is represented by the following chemical formula 7 (Chemical formula 7) (In the formula, each Z independently represents either an O or S atom, Ar 1 represents a divalent aromatic group, and n represents an integer of 2 to 100.)
- a hydrophilic oligomer is represented by the following chemical formula 8: (Chemical formula 8) Wherein X is H or a monovalent cation, Y is a sulfonyl group or a carbonyl group, and Z is O Or Ar 2 represents a divalent aromatic group, and m represents an integer of 2 to 100.
- a method for synthesizing a block copolymer comprising a structure represented by the formula:
- the aromatic chain extender is a perfluoro compound (however, it may contain a group selected from the group consisting of a cyano group, a sulfonyl group, a sulfinyl group, and a carbonyl group) (16 ) Synthesis method of the block copolymer polymer described in 1.).
- a reaction solution obtained by a synthesis reaction of a hydrophilic oligomer is used as a hydrophilic oligomer solution, and a reaction solution obtained by a synthesis reaction of a hydrophobic oligomer is used as a hydrophobic oligomer solution (21 ) A method for synthesizing the block copolymer.
- a molded article comprising the block copolymer of any one of (1) to (12) or the sulfonate group-containing segmented block copolymer obtained by the synthesis method of (13) to (22).
- a fuel cell comprising the block copolymer according to (1) to (12) or the sulfonate group-containing segmented block copolymer obtained by the synthesis method according to (13) to (22) Proton exchange membrane.
- a proton exchange membrane electrode assembly for a fuel cell using the fuel cell proton exchange membrane according to any one of (24), (27), and (28).
- the sulfonic acid group-containing block copolymer of the first invention of the present application and the sulfonic acid group-containing block copolymer obtained by the method for producing a sulfonic acid group-containing block copolymer of the second invention of the present application are outside the scope of the present invention.
- the sulfonated block copolymer is excellent in all of swellability, durability, and proton conductivity with respect to high-temperature water.
- the membrane made of the sulfonic acid group-containing block copolymer of the present invention has excellent methanol blocking properties, it is suitable not only for a fuel cell using hydrogen as a fuel but also for a proton exchange membrane of a direct methanol fuel cell.
- Example 1 shows the 1 H-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 1.
- the 13 C-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 1 is shown.
- 1 shows the 1 H-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 2.
- the 13 C-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 2 is shown.
- 1 shows the 1 H-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 17.
- 13 shows the 13 C-NMR spectrum of the sulfonic acid group-containing segmented block polymer obtained in Example 17.
- the first invention of the present application is a sulfonic acid group-containing segmented block copolymer having a specific polymer structure and its use.
- the sulfonic acid group-containing segmented block copolymer of the first invention of the present application is a block copolymer having at least one hydrophilic segment and hydrophobic segment in the molecule, and is represented by the following chemical formula 1.
- the logarithmic viscosity measured at 30 ° C. for a 0.5 g / dL solution using N-methyl-2-pyrrolidone as a solvent is in the range of 0.5 to 5.0 dL / g. Block copolymer.
- X is H or a monovalent cation
- Y is a sulfone group or a carbonyl group
- Z and Z ′ are each independently an O or S atom
- W is a direct bond between benzenes.
- Ar 1 and Ar 12 are each independently a divalent aromatic group
- n and m are each independently 2 to 100 Each represents an integer.
- X When used as a proton exchange membrane, it is preferable that X is H because proton conductivity increases. When processing and molding the polymer, it is preferable that X is a monovalent metal ion such as Na, K, Li, because the stability of the polymer is increased. X may be an organic cation such as monoamine. Y is preferably a sulfone group because the solubility of the polymer in a solvent tends to increase. Ar 1 and Ar 2 may independently be any known divalent group mainly composed of an aromatic group, but a preferred example is selected from the group represented by the following chemical formulas 3A to 3N A divalent aromatic group.
- R represents a methyl group
- p represents an integer of 0 to 2, respectively.
- Ar 1 and Ar 2 are each independently more preferably a structure represented by the chemical formulas 3A, 3C, 3E, 3F, 3K, 3M, and 3N, among the above chemical formulas 3A to 3N.
- a structure represented by 3F ′ is more preferred, and a structure represented by the chemical formula 3A ′ is also preferred.
- Ar 1 and Ar 2 may each independently comprise two or more types of structures selected from the structures represented by the above chemical formulas 3A to 3N.
- At least one of Z and Z ′ is preferably an O atom from the viewpoint of availability of raw materials and ease of synthesis. More preferably, both are O atoms. However, if it is an S atom, the oxidation resistance may be improved.
- W is a direct bond between benzene rings because the characteristics and durability of the film can be improved.
- W is a sulfone group, there is an advantage that side reactions during synthesis can be reduced.
- N is preferably in the range of 10 to 70 because the mechanical properties of the film are improved. If it is less than 10, the swellability may be excessively increased or the durability may be lowered. If it exceeds 70, it will be difficult to control the molecular weight, and it may be difficult to synthesize the polymer having the designed structure. More preferably, n is in the range of 20-60.
- m is in the range of 3 or more and less than 10 because a membrane suitable for a proton exchange membrane of a direct methanol fuel cell using methanol as fuel can be obtained. More preferably, m is in the range of 3-8. It is not preferred that m is less than 3 because only the same properties as a film made of a random copolymer can be obtained. If m is 10 or more, the methanol permeability may be too large.
- the polymer for obtaining a membrane suitable for a proton exchange membrane of a direct methanol fuel cell preferably has an m / n in the range of 0.4 to 1.0. If it is less than 0.4, the proton conductivity of the membrane may be significantly reduced. If it is 1.0 or more, the methanol permeability may be too large. More preferably, it is in the range of 0.5 to 0.8.
- m is in the range of 10 or more and less than 70 because a membrane suitable for a proton exchange membrane of a fuel cell using hydrogen as a fuel can be obtained. More preferably, m is in the range of 15 to 55. Even if m is less than 10, a polymer used for a proton exchange membrane for a fuel cell using hydrogen as a fuel can be synthesized, but sufficient improvement in characteristics may not be expected. When m is 70 or more, it may be difficult to synthesize a polymer used for a proton exchange membrane for a fuel cell using hydrogen as a fuel. However, when synthesis is possible, there is no problem even if m is 70 or more.
- m / n is preferably in the range of 0.4 to 1.5. If it is less than 0.4, the output of the fuel cell may be significantly reduced. If it is 1.5 or more, the swelling of the film may be remarkably increased. More preferably, it is in the range of 0.6 to 1.3.
- the sulfonic acid group-containing segmented block copolymer of the first invention of the present application can be synthesized by any known method. It can be synthesized also by combining oligomers that have been synthesized in advance and become hydrophilic and hydrophobic segments with a coupling agent. As an example, a method of coupling a hydroxyl group-terminated oligomer with a perfluoroaromatic compound such as decafluorobiphenyl can be mentioned. It can also be synthesized by modifying one end group of an oligomer that has been synthesized in advance to become a hydrophilic or hydrophobic segment with a highly reactive group and reacting with the other oligomer. .
- the oligomer may be used after being purified and isolated after synthesis, or may be used in the synthesized solution as it is, or the purified and isolated oligomer may be used as a solution.
- a method of previously synthesizing one of the terminal groups of the oligomer to be a hydrophilic and hydrophobic segment with a highly reactive group and reacting the other oligomer is preferable. In that case, it is preferable to react the modified oligomer and the other oligomer in equimolar amounts, but in order to prevent gelation due to side reactions during the reaction, it is better to keep the modified oligomer slightly in excess. Yes.
- the degree of excess varies depending on the molecular weight of the oligomer and the molecular weight of the target polymer, but is preferably in the range of 0.1 to 50 mol%, more preferably in the range of 0.5 to 10 mol%.
- the hydrophobic segment is preferably modified with a highly reactive group. Depending on the structure of the hydrophilic segment, the modification reaction may not proceed well.
- hydrophilic oligomer in the sulfonic acid group-containing segmented block copolymer of the first invention of the present application may be synthesized by reacting a sulfonated monomer represented by the following chemical formula 4 with various bisphenols or various bisthiophenols. it can.
- X represents H or a monovalent cation
- Y represents a sulfone group or a carbonyl group
- A represents a halogen element.
- X is preferably Na or K
- A is preferably F or Cl, respectively.
- various bisphenols or various bisthiophenols become excessive so that the terminal group of the oligomer becomes an OH group or an SH group.
- the degree of polymerization of the oligomer can be adjusted by the molar ratio of the monomer of Formula 4 and various bisphenols or various bisthiophenols.
- the monomer of Chemical formula 4 and various bisphenols or various bisthiophenols can be reacted by any known method, it is preferably reacted by an aromatic nucleophilic substitution reaction in the presence of a basic compound. .
- the reaction can be carried out in the range of 0 to 350 ° C., but is preferably carried out in the range of 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.
- the reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
- Examples of the solvent that can be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more.
- Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and aromatic bisphenols and aromatic bisthiophenols are active phenoxide structures and Anything can be used as long as it can have a thiophenoxide structure.
- X is potassium
- a potassium salt such as potassium carbonate
- a sodium salt such as sodium carbonate
- Water produced as a by-product should be removed by distillation with an azeotropic solvent such as toluene, or by using a water absorbing material such as molecular sieve, or by distillation with a polymerization solvent. Can do.
- the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably charged so that the resulting polymer concentration is 5 to 50% by weight, and more preferably in the range of 20 to 40% by weight.
- the polymerization solution may be used as it is for the synthesis of the block polymer, or may be used as a solution by removing by-products such as inorganic salts, or the polymer may be used after isolation and purification, but is preferred. Is a method for isolating and purifying polymers.
- the method for removing inorganic salts as by-products from the solution of the hydrophilic oligomer may be any known method such as filtration, decantation after centrifugal sedimentation, dialysis in water, or salting out in water. From the viewpoint of production efficiency and yield, filtration is preferable.
- the salt is removed by filtration or centrifugal sedimentation, the polymer can be recovered by dropping the solution into the non-solvent of the hydrophilic segment.
- dialysis the polymer can be recovered by evaporation to dryness, and in the case of salting out, the polymer can be recovered by filtration.
- the isolated hydrophilic oligomer is preferably purified by washing with a non-solvent, reprecipitation, dialysis or the like, and washing is preferred from the viewpoint of work efficiency and purification efficiency. It is preferable to remove the organic solvent used in the synthesis and purification as much as possible. The removal of the organic solvent is preferably carried out by drying, more preferably drying under reduced pressure at a temperature in the range of 10 to 150 ° C.
- the non-solvent of the hydrophilic oligomer can be selected from any organic solvent, but is preferably miscible with the aprotic polar solvent used in the reaction.
- Specific examples include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- hydrophobic oligomer in the sulfonic acid group-containing segmented block copolymer of the first invention of the present application is obtained by reacting a monomer represented by the following chemical formula 5A or 5B with various bisphenols or various bisthiophenols, and then formula 6A , 6B, 6C can be synthesized by reacting.
- the various bisphenols or various bisthiophenols be excessive so that the end groups of the oligomer are OH groups or SH groups.
- the degree of polymerization of the oligomer can be adjusted by the molar ratio of the monomer of the chemical formula 5A or 5B and various bisphenols or various bisthiophenols.
- the monomer of formula 5A or 5B and various bisphenols or various bisthiophenols can be reacted by any known method, but they can be reacted by an aromatic nucleophilic substitution reaction in the presence of a basic compound. Is preferred.
- the reaction can be carried out in the range of 0 to 350 ° C., but is preferably carried out in the range of 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.
- the reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
- Solvents that can be used include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, and sulfolane. It is not limited to this, and any material that can be used as a stable solvent in the aromatic nucleophilic substitution reaction may be used. These organic solvents may be used alone or as a mixture of two or more.
- aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, and sulfolane. It is not limited to this, and any material that can be used as a stable solvent in the aromatic nucleophilic substitution reaction may be used.
- These organic solvents may be used alone or as a mixture of two or more.
- Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and aromatic bisphenols and aromatic bisthiophenols are active phenoxide structures and Anything can be used as long as it can have a thiophenoxide structure.
- Water produced as a by-product should be removed by distillation with an azeotropic solvent such as toluene, or by using a water absorbing material such as molecular sieve, or by distillation with a polymerization solvent. Can do.
- the monomer When the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably charged so that the resulting polymer concentration is 1 to 20% by weight, and more preferably in the range of 5 to 15% by weight. When the amount is less than 1% by weight, the degree of polymerization tends to be difficult to increase. On the other hand, when it is more than 20% by weight, the reaction may be stopped due to precipitation due to the polymer structure.
- the compound of chemical formula 6A or 6B is reacted with the terminal groups derived from various bisphenols or various bisthiophenols. .
- the reaction may be carried out after once isolating the reaction product of the monomer of the chemical formula 5A or 5B and various bisphenols or various bisthiophenols, or the reaction solution may be used as it is. It is preferable to use the reaction solution as it is. At that time, inorganic salts produced as a by-product in the reaction may be removed by decantation or filtration.
- the compound of the above chemical formula 6A or 6B When the compound of the above chemical formula 6A or 6B is reacted with a terminal group derived from various bisphenols or various bisthiophenols, it is preferable to react the compound of the above chemical formula 6A or 6B in excess. More preferably, in a solution containing an excess of the compound of formula 6A or 6B, a reaction product of the monomer of formula 5A or 5B and various bisphenols or various bisthiophenols is added little by little and allowed to react. preferable. If a large amount is added at once or the chemical formula 6A or 6B is insufficient, the reaction solution may gel.
- the solvent used in the reaction may be any solvent in which each component dissolves.
- N-methyl-2-pyrrolidone N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, etc.
- aprotic polar solvent may include, but are not limited to, preferred examples.
- reaction temperature is preferably in the range of 50 to 150 ° C, more preferably in the range of 70 to 130 ° C.
- any known method such as dropping the oligomer into a non-solvent and washing can be used.
- the non-solvent for the oligomer water or any organic solvent can be selected. Water is preferred for removing inorganic salts.
- An organic solvent is preferred for removing the compound of formula 6A or 6B.
- the target to be dropped first may be either water or an organic solvent. It is preferable to remove the organic solvent used in the synthesis and purification as much as possible.
- the removal of the organic solvent is preferably carried out by drying, more preferably drying under reduced pressure at a temperature in the range of 10 to 150 ° C.
- the non-solvent organic solvent can be selected from any organic solvents, but is preferably miscible with the aprotic polar solvent used in the reaction.
- Specific examples include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- the segmented block copolymer can be obtained by reacting the hydrophobic oligomer and the hydrophilic oligomer synthesized as described above.
- the hydrophobic oligomer and the hydrophilic oligomer one or more oligomers selected from the group consisting of oligomers having different structures, molecular weights, molecular weight distributions, and terminal groups can be used.
- the molecular weight of each oligomer can be determined by any known method, but it is preferable to determine the number average molecular weight by quantifying the end groups.
- the hydrophobic oligomer in the present invention is characterized by having a benzonitrile structure, but due to its structure, the solubility in a solvent is poor. Therefore, when the NMR measurement does not dissolve in a suitable deuterated solvent, deuterated dimethyl sulfoxide is added to a solution dissolved in a normal solvent in which a hydrophobic oligomer is dissolved, such as N-methyl-2-pyrrolidone. It is preferable to measure by adding a deuterated solvent such as
- the sulfonic acid group in the hydrophilic oligomer is preferably an alkali metal salt, more preferably Na or K.
- an accurate molecular weight can be obtained by analyzing the composition in advance by elemental analysis. You may process with a metal salt and an alkali metal hydroxide, after processing with an excess acid once.
- the hydrophilic oligomer is preferably dried immediately before the synthesis of the block polymer to remove the adsorbed moisture. Drying may be performed by heating to 100 ° C. or higher, but drying under reduced pressure is more preferable.
- the molar ratio of hydrophilic oligomer to hydrophobic oligomer is preferably in the range of 0.9 to 1.1, more preferably in the range of 0.95 to 1.05.
- the degree of polymerization increases, but if it becomes too large, the subsequent handling may be hindered. Therefore, it is preferable to adjust the molar ratio appropriately.
- the oligomer which has a perfluorophenyl group at the terminal is made excessive. If the number of moles of the oligomer having a perfluorophenyl group at the end is extremely small, a gelation reaction may occur, which is not preferable.
- the reaction between the hydrophilic oligomer and the hydrophobic oligomer is carried out in an aprotic polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane. It is preferably carried out by reacting in the range of 50 to 150 ° C. in the presence of a basic compound such as potassium carbonate or sodium carbonate in an amount of 1 to 5 moles of the terminal phenol or thiophenol of the oligomer, 70 to 130 ° C. The range of is more preferable.
- an aprotic polar solvent such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane. It is preferably carried out by reacting in the range of 50 to 150
- the degree of polymerization may be adjusted by the molar ratio of the oligomer as described above, or the end point may be judged from the viscosity of the reaction solution, and the polymerization may be stopped by cooling or terminating the end.
- the reaction is preferably carried out under an inert gas stream such as nitrogen.
- the solid content concentration in the reaction solution may be in the range of 5 to 50% by weight, but if the hydrophobic oligomer is not dissolved, it may cause poor reactivity, and should be in the range of 5 to 20% by weight. Is preferred. Whether or not the hydrophobic oligomer is dissolved can be judged by whether it is transparent by visual inspection or not turbid.
- Isolation and purification of the polymer from the reaction solution can be performed by any known method.
- the polymer can be solidified by dropping the reaction solution into a non-solvent of a polymer such as water, acetone, or methanol.
- a polymer such as water, acetone, or methanol.
- water is preferable because it is easy to handle and inorganic salts can be removed.
- hot water at 60 ° C to 100 ° C, water and organic solvents (ketone solvents such as acetone, alcohol solvents such as methanol, ethanol, isopropanol) It is preferable to wash with a mixed solvent of
- X represents H or a monovalent cation
- n and m each independently represents an integer of 2 to 100.
- the second invention of the present application is a method for producing a sulfonic acid group-containing segmented block copolymer having a specific polymer structure and uses of the sulfonic acid group-containing segmented block copolymer.
- a sulfonic acid group-containing segmented block copolymer having a specific polymer structure uses of the sulfonic acid group-containing segmented block copolymer.
- the sulfonic acid group-containing segmented block polymer in the second invention of the present application is obtained by the following production method.
- the hydrophobic oligomer is represented by the following chemical formula 7: (Chemical formula 7) (In the formula, each Z independently represents either an O or S atom, Ar 1 represents a divalent aromatic group, and n represents an integer of 2 to 100.)
- a hydrophobic oligomer is represented by the following chemical formula 8: (Chemical formula 8) Wherein X is H or a monovalent cation, Y is a sulfonyl group or a carbonyl group, and Z is O Or Ar 2 represents a divalent aromatic group, and m represents an integer of 2 to 100. )
- the structure represented by this is contained in a molecule
- X When used as a proton exchange membrane, it is preferable that X is H because proton conductivity increases. When processing and molding the polymer, it is preferable that X is a monovalent metal ion such as Na, K, Li, because the stability of the polymer is increased. X may be an organic cation such as monoamine. Y is preferably a sulfonyl group because the solubility of the polymer in a solvent tends to increase. Ar 1 and Ar 2 may independently be any known divalent group mainly composed of an aromatic group, but a preferred example is selected from the group represented by the following chemical formulas 3A to 3N A divalent aromatic group.
- R represents a methyl group
- p represents an integer of 0 to 2, respectively.
- Ar 1 and Ar 2 are each independently more preferably a structure represented by the chemical formulas 3A, 3C, 3E, 3F, 3K, 3M, and 3N, among the above chemical formulas 3A to 3N.
- a structure represented by 3F ′ is more preferred, and a structure represented by the chemical formula 3A ′ is also preferred.
- Ar 1 and Ar 2 may each independently comprise two or more types of structures selected from the structures represented by the above chemical formulas 3A to 3N. In that case, it is preferable to have at least the structure of the following chemical formula 3A ′.
- At least one of Z and Z ′ is preferably an O atom from the viewpoint of availability of raw materials and ease of synthesis. More preferably, both are O atoms. However, if it is an S atom, the oxidation resistance may be improved.
- N is preferably in the range of 20 to 70 because the mechanical properties of the film are improved. If it is less than 20, the swellability may become too large or the durability may be lowered. If it exceeds 70, it will be difficult to control the molecular weight, and it may be difficult to synthesize the polymer having the designed structure. More preferably, n is in the range of 30-60.
- m is in the range of 3 or more and less than 25, a membrane suitable for a proton exchange membrane of a direct methanol fuel cell using methanol as fuel can be obtained. More preferably, m is in the range of 3-20. It is not preferred that m is less than 3 because only the same properties as a film made of a random copolymer can be obtained. If m is 25 or more, it is difficult to synthesize a polymer that can be applied to a direct methanol fuel cell. However, when synthesis is possible, there is no problem even if m is 25 or more.
- m is in the range of 25 or more and less than 70, it is preferable because a membrane suitable for a proton exchange membrane of a fuel cell using hydrogen as a fuel can be obtained. More preferably, m is in the range of 30-60. Even if m is less than 25, a polymer used for a proton exchange membrane for a fuel cell using hydrogen as a fuel can be synthesized, but sufficient improvement in properties may not be expected. When m is 70 or more, it may be difficult to synthesize a polymer used for a proton exchange membrane for a fuel cell using hydrogen as a fuel. However, when synthesis is possible, there is no problem even if m is 70 or more.
- the chain extender and the oligomer are charged in equimolar amounts, or the chain extender is A slight excess is preferred.
- the degree of excess varies depending on the molecular weight of the oligomer and the molecular weight of the target polymer, but is preferably in the range of 0 to 50 mol%, more preferably in the range of 0 to 10 mol%.
- hydrophilic oligomer in the sulfonic acid group-containing segmented block copolymer of the second invention of the present application may be synthesized by reacting a sulfonated monomer represented by the following chemical formula 4 with various bisphenols or various bisthiophenols. it can. Furthermore, in addition to the sulfonated monomer represented by the following chemical formula 4, it reacts with various bisphenols or various bisthiophenols using a dihalide such as 4,4′-dichlorodiphenylsulfone or 2,6-dichlorobenzonitrile. May be synthesized.
- a dihalide such as 4,4′-dichlorodiphenylsulfone or 2,6-dichlorobenzonitrile. May be synthesized.
- X represents H or a monovalent cation
- Y represents a sulfone group or a carbonyl group
- A represents a halogen element.
- X is preferably Na or K
- A is preferably F or Cl, respectively.
- various bisphenols or various bisthiophenols become excessive so that the terminal group of the oligomer becomes an OH group or an SH group.
- the degree of polymerization of the oligomer can be adjusted by the molar ratio of the monomer of Formula 4 and various bisphenols or various bisthiophenols.
- the monomer of Chemical formula 4 and various bisphenols or various bisthiophenols can be reacted by any known method, it is preferably reacted by an aromatic nucleophilic substitution reaction in the presence of a basic compound. .
- the reaction can be carried out in the range of 0 to 350 ° C., but is preferably carried out in the range of 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.
- the reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
- Examples of the solvent that can be used include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenyl sulfone, sulfolane, and the like. And any solvent that can be used as a stable solvent in the aromatic nucleophilic substitution reaction. These organic solvents may be used alone or as a mixture of two or more.
- Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and aromatic bisphenols and aromatic bisthiophenols are active phenoxide structures and Anything can be used as long as it can have a thiophenoxide structure.
- Water produced as a by-product should be removed by distillation with an azeotropic solvent such as toluene, or by using a water absorbing material such as molecular sieve, or by distillation with a polymerization solvent. Can do.
- the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably charged so that the resulting polymer concentration is 5 to 50% by weight, and more preferably in the range of 20 to 40% by weight.
- the amount is less than 5% by weight, the degree of polymerization tends to be difficult to increase.
- the amount is more than 50% by weight, the viscosity of the reaction system becomes too high and the post-treatment of the reaction product tends to be difficult.
- the method for removing inorganic salts as by-products from the solution of the hydrophilic oligomer may be any known method such as filtration, decantation after centrifugal sedimentation, dialysis in water, or salting out in water. From the viewpoint of production efficiency and yield, filtration is preferable.
- the salt is removed by filtration or centrifugal sedimentation, the polymer can be recovered by dropping the solution into the non-solvent of the hydrophilic segment.
- dialysis the polymer can be recovered by evaporation to dryness, and in the case of salting out, the polymer can be recovered by filtration.
- the isolated hydrophilic oligomer is preferably purified by washing with a non-solvent, reprecipitation, dialysis or the like, and washing is preferred from the viewpoint of work efficiency and purification efficiency. It is preferable to remove the organic solvent used in the synthesis and purification as much as possible. The removal of the organic solvent is preferably carried out by drying, more preferably drying under reduced pressure at a temperature in the range of 10 to 150 ° C.
- the non-solvent of the hydrophilic oligomer can be selected from any organic solvent, but is preferably miscible with the aprotic polar solvent used in the reaction.
- Specific examples include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- hydrophobic oligomer in the sulfonic acid group-containing segmented block copolymer of the second invention of the present application is synthesized by reacting a monomer represented by the following chemical formula 5A or 5B with various bisphenols or various bisthiophenols. Can do.
- the various bisphenols or various bisthiophenols be excessive so that the end groups of the oligomer are OH groups or SH groups.
- the degree of polymerization of the oligomer can be adjusted by the molar ratio of the monomer of the chemical formula 5A or 5B and various bisphenols or various bisthiophenols.
- the monomer of formula 5A or 5B and various bisphenols or various bisthiophenols can be reacted by any known method, but they can be reacted by an aromatic nucleophilic substitution reaction in the presence of a basic compound. Is preferred.
- the reaction can be carried out in the range of 0 to 350 ° C., but is preferably carried out in the range of 50 to 250 ° C. When the temperature is lower than 0 ° C., the reaction does not proceed sufficiently, and when the temperature is higher than 350 ° C., the polymer tends to be decomposed.
- the reaction can be carried out in the absence of a solvent, but is preferably carried out in a solvent.
- Solvents that can be used include aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, and sulfolane. It is not limited to this, and any material that can be used as a stable solvent in the aromatic nucleophilic substitution reaction may be used. These organic solvents may be used alone or as a mixture of two or more.
- aprotic polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, and sulfolane. It is not limited to this, and any material that can be used as a stable solvent in the aromatic nucleophilic substitution reaction may be used.
- These organic solvents may be used alone or as a mixture of two or more.
- Examples of the basic compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, and aromatic bisphenols and aromatic bisthiophenols are active phenoxide structures and Anything can be used as long as it can have a thiophenoxide structure.
- Water produced as a by-product should be removed by distillation with an azeotropic solvent such as toluene, or by using a water absorbing material such as molecular sieve, or by distillation with a polymerization solvent. Can do.
- the monomer When the aromatic nucleophilic substitution reaction is carried out in a solvent, the monomer is preferably charged so that the resulting polymer concentration is 1 to 25% by weight, and more preferably in the range of 5 to 15% by weight.
- the amount is less than 1% by weight, the degree of polymerization tends to be difficult to increase.
- the amount is more than 25% by weight, the reaction may be stopped due to precipitation due to the polymer structure.
- any known method such as dropping the oligomer into a non-solvent and washing can be used.
- the non-solvent for the oligomer water or any organic solvent can be selected. Water is preferred for removing inorganic salts.
- the target to be dropped first may be either water or an organic solvent. It is preferable to remove the organic solvent used in the synthesis and purification as much as possible.
- the removal of the organic solvent is preferably carried out by drying, more preferably drying under reduced pressure at a temperature in the range of 10 to 150 ° C.
- the non-solvent organic solvent can be selected from any organic solvents, but is preferably miscible with the aprotic polar solvent used in the reaction.
- Specific examples include ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono, and alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, dipropyl ketone, diisopropyl ketone, and cyclohexanono
- alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol.
- the segmented block copolymer can be obtained by reacting the hydrophobic oligomer and the hydrophilic oligomer synthesized as described above with a chain extender.
- a chain extender As the hydrophobic oligomer and the hydrophilic oligomer, one or more oligomers selected from the group consisting of oligomers having different structures, molecular weights, and molecular weight distributions can be used.
- the molecular weight of each oligomer can be determined by any known method, but it is preferable to determine the number average molecular weight by quantifying the end groups.
- the hydrophobic oligomer in the present invention is characterized by having a benzonitrile structure, but due to its structure, the solubility in a solvent is poor. Therefore, when the NMR measurement does not dissolve in a suitable deuterated solvent, deuterated dimethyl sulfoxide is added to a solution dissolved in a normal solvent in which a hydrophobic oligomer is dissolved, such as N-methyl-2-pyrrolidone. It is preferable to measure by adding a deuterated solvent such as
- the sulfonic acid group in the hydrophilic oligomer is preferably an alkali metal salt, more preferably Na or K.
- an accurate molecular weight can be obtained by analyzing the composition in advance by elemental analysis. You may process with a metal salt and an alkali metal hydroxide, after processing with an excess acid once.
- the hydrophilic oligomer is preferably dried immediately before the synthesis of the block polymer to remove the adsorbed moisture. Drying may be performed by heating to 100 ° C. or higher, but drying under reduced pressure is more preferable.
- an aromatic chain extender in which the halogen is fluorine is preferable because when the halogen is fluorine, side reactions such as a decrease in segment length and high reactivity can be suppressed.
- the aromatic chain extender in which halogen is fluorine preferably has 3 or more fluorine atoms in one molecule, more preferably 2 or more fluorine atoms are adjacent to each other, A perfluoro compound is preferable because of higher reactivity.
- the aromatic chain extender in which the halogen is fluorine may have an electron-withdrawing property as a substituent, and the electron-withdrawing group is preferably in the ortho position or the para position with respect to the fluorine atom.
- Examples of the electron-withdrawing group include, but are not limited to, a cyano group, a sulfonyl group, a sulfinyl group, and a carbonyl group.
- Preferred examples of the aromatic chain extender in which the halogen is fluorine include a single aromatic ring (which may have an electron-withdrawing group as a substituent), or a plurality of aromatic groups having an electron-withdrawing group.
- Examples thereof include compounds in which the aromatic ring linked with is perfluorinated, and more specifically, any of hexafluorobenzene, decafluorobiphenyl, decafluorobenzophenone, decafluorodiphenyl sulfone, and pentafluorobenzonitrile. Or mixtures thereof.
- compounds in which some of the fluorine atoms are substituted should also be used within a range that satisfies the above requirements. Can do.
- substituent for the fluorine atom examples include a hydrogen atom, other halogen atoms such as chlorine, bromine and iodine, and hydrocarbon groups such as a phenoxy group, a phenyl group and a methyl group, but are not limited thereto. It is not a thing.
- hydrophilic oligomer, hydrophobic oligomer and chain extender is aprotic polarity such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, diphenylsulfone, sulfolane
- the reaction is preferably carried out in a solvent in the range of 50 to 160 ° C. in the presence of a basic compound such as potassium carbonate or potassium carbonate in an amount of 1 to 5 moles of the oligomeric phenol or thiophenol end, 70 A range of ⁇ 130 ° C. is more preferable.
- the degree of polymerization may be adjusted by the molar ratio of the oligomer as described above, and the hydrophilic and hydrophobic contents may also be adjusted by the molar ratio of the oligomer.
- the end point may be determined from the viscosity of the reaction solution, and the polymerization may be stopped by cooling or stopping the end.
- the reaction is preferably carried out under an inert gas stream such as nitrogen.
- the solid content concentration in the reaction solution may be in the range of 1 to 25% by weight, but it is preferably in the range of 5 to 20% by weight in consideration of poor reactivity and poor solubility of the hydrophobic oligomer. . More preferably, it is in the range of 8 to 15% by weight.
- the solid content concentration here refers to the polymer concentration in the solution. Whether or not the hydrophobic oligomer is dissolved can be judged by whether it is transparent by visual inspection or not turbid.
- the polymerization of the segmented block polymer may be performed by mixing the polymerization solution of each oligomer as it is without performing the purification as described above or in a state where by-products such as inorganic salts are removed. Specifically, each oligomer polymerization solution is mixed without isolating / purifying the polymer from the oligomer polymerization solution or with only by-products such as inorganic salts removed from the solution, and a chain extender is added.
- the reaction can be carried out in the presence of a basic compound such as potassium carbonate or sodium carbonate.
- the polymerization is preferably carried out by reacting in the range of 50 to 160 ° C, more preferably in the range of 70 to 130 ° C.
- the degree of polymerization may be adjusted by the molar ratio of the oligomer, and the hydrophilic and hydrophobic contents may also be adjusted by the molar ratio of the oligomer.
- the end point may be determined from the viscosity of the reaction solution, and the polymerization may be stopped by cooling or stopping the end.
- the reaction is preferably carried out under an inert gas stream such as nitrogen.
- the solid content concentration in the reaction solution may be in the range of 1 to 25% by weight, but it is preferably in the range of 5 to 20% by weight in consideration of poor reactivity and poor solubility of the hydrophobic oligomer. . More preferably, it is in the range of 8 to 15% by weight. Whether or not the hydrophobic oligomer is precipitated can be judged by whether it is transparent or not turbid by visual observation.
- Isolation and purification of the polymer from the reaction solution can be performed by any known method.
- the polymer can be solidified by dropping the reaction solution into a non-solvent of a polymer such as water, acetone, or methanol.
- a polymer such as water, acetone, or methanol.
- water is preferable because it is easy to handle and inorganic salts can be removed.
- hot water at 60 ° C to 100 ° C, water and organic solvents (ketone solvents such as acetone, alcohol solvents such as methanol, ethanol, isopropanol) It is preferable to wash with a mixed solvent of
- the ion exchange capacity of the segmented block copolymer is preferably 0.5 to 2.7 meq / g. If it is 0.5 meq / g or less, the proton conductivity is too low, which is not preferable. 2.7 meq / g or more is not preferable because swelling increases and durability decreases. When it is in the range of 0.7 to 2.0 meq / g, it has more preferable characteristics such as proton conductivity and swelling resistance. Further, when it is in the range of 0.7 to 1.6 meq / g, the methanol permeability is small, so that it is particularly suitable for a proton exchange membrane for a direct methanol fuel cell.
- the molecular weight of the sulfonic acid group-containing block copolymer of the present invention is 0.5 or more when expressed in terms of logarithmic viscosity when a 0.5 g / dL N-methyl-2-pyrrolidone solution is measured at 30 ° C. Is preferable from the viewpoint of physical properties, more preferably 0.9 or more, and further preferably 1.2 or more. If it is less than 0.5, the physical properties are remarkably deteriorated. When the logarithmic viscosity is more than 5.0, the viscosity of the solution in which the polymer is dissolved may be extremely high, and handling may be difficult.
- the sulfonic acid group-containing block copolymer in the first and second inventions of the present application can be used as a composition by mixing other substances and compounds.
- materials to be mixed include fibrous substances, heteropolyacids such as phosphotungstic acid and phosphomolybdic acid, acidic compounds such as low molecular weight sulfonic acid, phosphonic acid, and phosphoric acid derivatives, silicic acid compounds, and zirconium phosphoric acid. Can be mentioned.
- the content of the mixture is preferably less than 50% by mass. If it is 50% by mass or more, the physical properties of moldability are impaired, which is not preferable.
- a fibrous substance is preferable for suppressing swelling, and an inorganic fibrous substance such as potassium titanate fiber is more preferable.
- polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate
- polyamides such as nylon 6, nylon 6,6, nylon 6,10, and nylon 12, polymethyl methacrylate, and polymethacrylate.
- Acrylate resins such as polymethyl acrylate, polyacrylic acid esters, polyacrylic acid resins, polymethacrylic acid resins, polyethylene, polypropylene, various polyolefins including polystyrene and diene polymers, polyurethane resins, cellulose acetate, Cellulosic resins such as ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether Heat curing of aromatic polymers such as sulfone, polyether ether ketone, polyether imide, polyimide, polyamide imide, polybenzimidazole, polybenzoxazole, polybenzthiazole, epoxy resin, phenol resin, novolac resin, benzoxazine resin Resin etc. can be used.
- the sulfonic acid group-containing block copolymer polymer of the present invention is preferably contained in an amount of 50% by mass or more and less than 100% by mass of the entire composition. More preferably, it is 70 mass% or more and less than 100 mass%.
- the content of the sulfonic acid group-containing block copolymer polymer of the present invention is less than 50% by mass of the entire composition, the sulfonic acid group concentration of the proton exchange membrane containing this composition is lowered and good proton conductivity is obtained.
- the unit containing a sulfonic acid group tends to be a discontinuous phase and the mobility of ions to be conducted tends to decrease.
- composition of the present invention if necessary, for example, an antioxidant, a heat stabilizer, a lubricant, a tackifier, a plasticizer, a crosslinking agent, a viscosity modifier, an antistatic agent, an antibacterial agent, an antifoaming agent, Various additives such as a dispersant and a polymerization inhibitor may be included.
- the sulfonic acid group-containing block copolymer polymer can be used as a composition in a solution dissolved in an appropriate solvent.
- an appropriate one is selected from aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, diphenylsulfone, N-methyl-2-pyrrolidone, hexamethylphosphonamide and the like.
- the present invention is not limited to these. Among these, it is preferable to dissolve in N-methyl-2-pyrrolidone, N, N-dimethylacetamide and the like.
- a plurality of these solvents may be used as a mixture within a possible range.
- the concentration of the compound in the solution is preferably in the range of 0.1 to 50% by weight, more preferably in the range of 5 to 20% by weight, and still more preferably in the range of 5 to 15% by weight. If the compound concentration in the solution is less than 0.1% by mass, it tends to be difficult to obtain a good molded product, and if it exceeds 50% by mass, the workability tends to deteriorate. You may mix and use the above-mentioned compound etc. in a solution.
- the sulfonic acid group of the polymer in the sulfonic acid group-containing block copolymer polymer composition in the first and second inventions of the present application may be an acid or a salt with a cation. From the viewpoint of properties, a salt with a cation is preferred. When it is a salt, it can be converted to an acid by acid treatment as necessary, such as after molding.
- the sulfonic acid group-containing block copolymer polymer and the composition thereof according to the first and second inventions of the present application can be formed into a molded body such as a fiber or a film by any method such as extrusion, spinning, rolling or casting. Among these, it is preferable to mold from a solution dissolved in an appropriate solvent.
- the method of obtaining a molded body from a solution can be performed using a conventionally known method.
- the molded product can be obtained by removing the solvent by heating, drying under reduced pressure, immersion in a compound non-solvent that can be mixed with a solvent that dissolves the compound, or the like.
- the solvent is an organic solvent
- the solvent is preferably distilled off by heating or drying under reduced pressure.
- it can be formed into various shapes such as a fiber shape, a film shape, a pellet shape, a plate shape, a rod shape, a pipe shape, a ball shape, and a block shape in a composite form with other compounds as necessary.
- the sulfonic acid group in the molded article thus obtained may contain a salt form with a cation, but if necessary, it can be converted to a free sulfonic acid group by acid treatment. You can also.
- An ion conductive membrane can also be produced from the sulfonic acid group-containing block copolymer polymer and the composition thereof in the first and second inventions of the present application.
- the ion conductive membrane is not limited to the sulfonic acid group-containing copolymer of the present invention, and may be a composite membrane with a support such as a porous membrane, a nonwoven fabric, fibril, or paper.
- the obtained ion conductive membrane can be used as a proton exchange membrane for a fuel cell.
- the most preferable method for forming the ion conductive membrane is a cast from a solution, and the ion conductive membrane can be obtained by removing the solvent from the cast solution as described above.
- the removal of the solvent is preferably by drying from the uniformity of the ion conductive membrane.
- it can also dry at the lowest temperature possible under reduced pressure.
- the viscosity of the solution is high, when the substrate or the solution is heated and cast at a high temperature, the viscosity of the solution is lowered and the casting can be easily performed.
- the thickness of the solution at the time of casting is not particularly limited, but is preferably 10 to 1000 ⁇ m.
- the thickness of the solution is thinner than 10 ⁇ m, the form as an ion conductive film tends to be not maintained, and if it is thicker than 1000 ⁇ m, a non-uniform ion conductive film tends to be easily formed.
- a method for controlling the cast thickness of the solution a known method can be used.
- the thickness can be controlled by the amount and concentration of the solution by making the thickness constant using an applicator, a doctor blade or the like, or making the cast area constant using a glass petri dish or the like.
- the cast solution can obtain a more uniform film by adjusting the solvent removal rate.
- the evaporation rate can be reduced by lowering the temperature in the first stage.
- the coagulation rate of the compound can be adjusted by leaving the solution in air or an inert gas for an appropriate time.
- the proton exchange membrane in the first and second inventions of the present application can have any film thickness depending on the purpose, but is preferably as thin as possible from the viewpoint of proton conductivity. Specifically, it is preferably 5 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and most preferably 20 to 80 ⁇ m. If the thickness of the proton exchange membrane is less than 5 ⁇ m, handling of the proton exchange membrane becomes difficult and a short circuit or the like tends to occur when a fuel cell is produced. If the thickness of the proton exchange membrane is greater than 200 ⁇ m, the electric resistance value of the proton exchange membrane increases. There is a tendency for the power generation performance of the to decrease.
- the sulfonic acid group in the membrane may contain a metal salt, but can be converted to free sulfonic acid by an appropriate acid treatment. In this case, it is also effective to immerse the film obtained in an aqueous solution of sulfuric acid, hydrochloric acid, etc. with or without heating.
- the proton conductivity of the proton exchange membrane is preferably 1.0 ⁇ 10 ⁇ 3 S / cm or more. When the proton conductivity of 1.0 ⁇ 10 -3 S / cm or higher, tend to better output is obtained in the fuel cell using the proton exchange membrane, 1.0 ⁇ 10 -3 S / When it is less than cm, the output of the fuel cell tends to decrease.
- the swellability is as small as possible. If the swellability is too large, the film strength is lowered, and the durability may be lowered. However, if the amount is too small, necessary proton conductivity may not be obtained, which is not preferable.
- the water absorption rate weight% of water absorbed relative to the dry weight of polymer is shown as an example of the value when the preferred range of swelling is treated with hot water at 80 ° C.
- the area swelling ratio (the ratio of the increase in area due to swelling to the area of the film before swelling) is preferably 20 to 130% by weight, more preferably 30 to 110% by weight. Is preferably in the range of 0 to 15%, and more preferably in the range of 0 to 15%.
- Swellability can be adjusted by the amount of sulfonic acid groups in the polymer, the chain length of the hydrophilic segment, the chain length of the hydrophobic segment, and the like. Increasing the amount of sulfonic acid groups can increase water absorption, and increasing the hydrophilic segment chain length can further increase water absorption. By reducing the amount of sulfonic acid groups or increasing the chain length of the hydrophobic segment, the area swelling rate can be reduced.
- the swelling property of the film can also be controlled by the process conditions (drying temperature, drying speed, solution concentration, solvent composition) for producing the film from the polymer.
- phase separation structure In order to form a phase separation structure, it is usually only necessary to form a film by the method as described above, but for the purpose of promoting phase separation, a film is formed by adding a non-solvent such as water to the polymer solution. You can also.
- a joined body of the proton exchange membrane or film of the present invention and the electrode can be obtained.
- a method for producing this joined body a conventionally known method can be used.
- an adhesive is applied to the electrode surface and the proton exchange membrane and the electrode are bonded, or the proton exchange membrane and the electrode are bonded.
- the method of applying and bonding the sulfonic acid group-containing polyarylene ether compound of the present invention and an adhesive mainly comprising the composition to the electrode surface is preferable. This is because the adhesion between the proton exchange membrane and the electrode is improved, and it is considered that the proton conductivity of the proton exchange membrane is less impaired.
- the proton exchange membrane or film of the present invention is excellent in heat resistance, processability, and proton conductivity, so that it can withstand operation at high temperatures, is easy to produce, and has a good output. Can be provided.
- the proton exchange membrane of the present invention is suitable not only for polymer electrolyte fuel cells (PEFC) using hydrogen as fuel, but also for methanol direct fuel cells (DMFC) using methanol as fuel because of its low methanol permeability. ing.
- PEFC polymer electrolyte fuel cells
- DMFC methanol direct fuel cells
- it is also suitable for a fuel cell of a type in which hydrogen is taken out from a hydrocarbon such as methanol, gasoline, ether, etc. by a reformer.
- the sulfonic acid group-containing segmented block copolymer in the first and second inventions of the present application can also be used as a binder for an electrode catalyst in a fuel cell. Compared to conventional binders, an excellent electrode can be obtained due to high durability and excellent proton conductivity.
- Solvents include aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, sulfolane, diphenylsulfone, N-methyl-2-pyrrolidone, hexamethylphosphonamide, methanol, ethanol, etc.
- Alcohols such as dimethyl ether and ethylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone and cyclohexanone, a mixed solvent of these organic solvents and water, and the like can be used.
- ⁇ Proton conductivity> A platinum wire (diameter: 0.2 mm) was pressed against the surface of the strip-shaped membrane sample on a self-made measuring probe (manufactured by Teflon (registered trademark)), and a constant temperature / humidity oven at 80 ° C. and 95% RH (Nagano Science Co., Ltd. The sample was held in Machine Works, LH-20-01), and the impedance between the platinum wires was measured by SOLARTRON 1250 FREQUENCY RESPONSE ANALYSER.
- ⁇ NMR measurement> A polymer (a sulfonic acid group is Na or K salt) was dissolved in a solvent, and 1 H-NMR was measured at room temperature and 13 C-NMR was measured at 70 ° C. using UNITY-500 manufactured by VARIAN.
- the solvent a mixed solvent of N-methyl-2-pyrrolidone and heavy dimethyl sulfoxide (85/15 vol./vol.) was used.
- the hydrophilic oligomer and the hydrophobic oligomer constituting the hydrophilic segment and the hydrophobic segment, respectively, are measured by 1 H-NMR spectrum, and the number average molecular weight is calculated from the integral ratio of the peak derived from the end group and the peak of the skeleton part. Asked.
- the proton peak at the ortho position of the ether bond in the biphenyl structure is detected at 7.2 ppm from the end group (where it is bonded to perfluorobiphenyl). Since the amount in the skeleton was detected at 7.3 ppm, the number average molecular weight was determined from the integration ratio of these peaks.
- the peak of the proton at the ortho position of the ether bond in the biphenyl structure is 6.8 ppm from the terminal group (ortho position of the phenolic hydroxyl group), and the skeleton Since those in the middle were detected at 7.3 ppm, the number average molecular weight was determined from the integration ratio of these peaks.
- the composition ratio of the hydrophilic segment to the hydrophobic segment was analyzed by 1 H-NMR, and the presence or absence of a decrease in the segment length was analyzed by 13 C-NMR.
- ⁇ Swellability evaluation> A proton exchange membrane that had been left in a room at 23 ° C. and 50% RH for one day was cut out in a 50 mm square, and then immersed in hot water at 80 ° C. for 24 hours. After soaking, the dimensions and weight of the membrane were quickly measured. The membrane was dried at 120 ° C. for 3 hours, and the dry weight was measured. The water absorption rate and area swelling rate were calculated according to the following formula. The size of the film was measured by measuring the length of two orthogonal sides connected to a specific vertex.
- ⁇ Proton exchange membrane production method A> Dissolve 2.0 g of a polymer (having a sulfonic acid group in a salt form) in 18 mL of N-methyl-2-pyrrolidone (abbreviation: NMP), cast it on a glass plate with a thickness of 500 ⁇ m using an applicator, and It was dried by heating at 150 ° C. for 1 hour for 1 hour. Thereafter, the glass plate was allowed to cool to near room temperature, and the membrane was peeled off with water attached to the membrane.
- NMP N-methyl-2-pyrrolidone
- the peeled membrane is immersed in pure water, and then immersed in 1N sulfuric acid for 1 hour to convert the sulfonic acid group into an acid form, washed with pure water to remove free sulfuric acid, and air-dried to obtain a proton exchange membrane. It was.
- NMP N-methyl-2-pyrrolidone
- the obtained membrane was continuously immersed in pure water in a state of being attached to a polyethylene terephthalate film, and then continuously immersed in a 1 mol / L sulfuric acid aqueous solution for 30 minutes to convert the sulfonic acid group into an acid form. It was converted, washed with pure water to remove free sulfuric acid, dried, and peeled from a polyethylene terephthalate film to obtain a proton exchange membrane.
- the reaction solution was cooled to room temperature, poured into 3000 mL of pure water to solidify the oligomer, and further washed with pure water three times to remove NMP and inorganic salts.
- the oligomer washed with water was separated by filtration, dried at 100 ° C. for 2 hours, cooled to room temperature, and washed twice with 3000 mL of acetone to remove excess perfluorobiphenyl.
- the oligomer was again filtered off and dried under reduced pressure at 120 ° C. for 16 hours to obtain hydrophobic oligomer A.
- the number average molecular weight determined by 1 H-NMR measurement was 13880.
- the chemical structure of hydrophobic oligomer A is shown below.
- NMP 200 mL and 8.09 g of perfluorobiphenyl were placed and stirred at 110 ° C. in an oil bath while stirring under a nitrogen stream. Heated. There, the reaction solution of DCBN and BP was added over 2 hours with stirring using a dropping funnel, and the mixture was further stirred for 3 hours after completion of the addition. The reaction solution was cooled to room temperature and then poured into 3000 mL of acetone to solidify the oligomer.
- hydrophobic oligomer B The number average molecular weight determined by 1 H-NMR measurement was 11260. The chemical structure of hydrophobic oligomer B is shown below.
- Hydrophobic oligomer C was synthesized in the same manner as in Synthesis Example 1 except that 5.78 g of perfluorodiphenyl sulfone was used instead of 4.85 g of perfluorobiphenyl.
- the number average molecular weight determined by 1 H-NMR measurement was 14010.
- the chemical structure of hydrophobic oligomer C is shown below.
- NMP 200 mL and perfluorobiphenyl 30.09 g were placed and stirred at 110 ° C. in an oil bath under nitrogen flow. Heated. There, the reaction solution of DCBN and BP was added over 2 hours with stirring using a dropping funnel, and the mixture was further stirred for 3 hours after completion of the addition. The reaction solution was cooled to room temperature and then poured into 3000 mL of acetone to solidify the oligomer. The supernatant containing fine precipitates was removed, and further washed twice with acetone and then washed three times with pure water to remove NMP and inorganic salts.
- hydrophobic oligomer E was filtered off and dried under reduced pressure at 120 ° C. for 16 hours to obtain a hydrophobic oligomer E.
- the number average molecular weight determined by 1 H-NMR measurement was 5810.
- the chemical structure of the hydrophobic oligomer H is shown below.
- Hydrophobic oligomer I was synthesized in the same manner as in Synthesis Example 1 except that 5.26 g of perfluorobenzophenone was used instead of 4.85 g of perfluorobiphenyl. The number average molecular weight determined by 1 H-NMR measurement was 13050. The chemical structure of hydrophobic oligomer I is shown below.
- hydrophilic oligomer A After dehydration by azeotropy with toluene at 140 ° C., all toluene was distilled off. Then, it heated up at 200 degreeC and heated for 16 hours. Subsequently, 500 mL of NMP was added and cooled to room temperature while stirring. The obtained solution was subjected to suction filtration with a 25G2 glass filter, whereby a yellow transparent solution was obtained. The obtained solution was dropped into 3 L of acetone to solidify the oligomer. The oligomer was further washed three times with acetone, then filtered and dried under reduced pressure to obtain hydrophilic oligomer A. The number average molecular weight determined by 1 H-NMR measurement was 25560. The chemical structure of hydrophilic oligomer A is shown below.
- hydrophilic oligomer D > S-DCDPS 250.0 g (508.9 mmol), BFP 175.09 g (523.0 mmol), sodium carbonate 66.23 g (624.9 mmol), NMP 800 mL, toluene 150 mL, nitrogen introduction tube, stirring blade, Dean-Stark trap, thermometer was added to a 2000 mL branch flask and hydrophilic oligomer D was obtained in the same manner as in Synthesis Example 6. The number average molecular weight determined by 1 H-NMR measurement was 24380. The chemical structure of the hydrophilic oligomer D is shown below.
- hydrophilic oligomer E > Sodium 4,4′-dichlorobenzophenone-3,3-disulfonate 231.7 g (508.9 mmol), BP 97.04 g (520.7 mmol), sodium carbonate 66.23 g (624.9 mmol), NMP 800 mL, toluene 150 mL, A hydrophilic oligomer E was obtained in the same manner as in Synthesis Example 6 in a 2000 mL branch flask equipped with a nitrogen introduction tube, a stirring blade, a Dean-Stark trap, and a thermometer. The number average molecular weight determined by 1 H-NMR measurement was 23530. The chemical structure of hydrophilic oligomer E is shown below.
- hydrophilic oligomer H > S-DCDPS 250.0 g (508.9 mmol), BP 106.18 g (570.2 mmol), sodium carbonate 69.50 g (655.8 mmol), NMP 650 mL, toluene 150 mL, nitrogen introduction tube, stirring blade, Dean-Stark trap, thermometer was added to a 2000 mL branch flask, and hydrophilic oligomer H was obtained in the same manner as in Synthesis Example 6. The number average molecular weight determined by 1 H-NMR measurement was 3890. The chemical structure of the hydrophilic oligomer H is shown below.
- Example 1 45.00 g of hydrophilic oligomer A, 24.61 g of hydrophobic oligomer A, 0.28 g of sodium carbonate, and 400 mL of NMP were placed in a 1000 mL branch flask equipped with a nitrogen introduction tube, a stirring blade, a Dean-Stark trap, and a thermometer. The mixture was stirred and dissolved in an oil bath at 50 ° C. Then, it heated to 110 degreeC and made it react for 10 hours. Thereafter, the polymer was cooled to room temperature and dropped into 3 L of pure water to solidify the polymer. After washing with pure water three times, it was treated at 80 ° C.
- Example 2 A sulfonic acid group-containing segmented block polymer B was obtained in the same manner as in Example 1 using 42.27 g of hydrophilic oligomer B, 18.72 g of hydrophobic oligomer A, 0.37 g of sodium carbonate, and 350 mL of NMP. The logarithmic viscosity of polymer B was 2.6 dL / g. A proton exchange membrane B was obtained from the obtained polymer by the above method. The chemical structure of polymer B is the same as polymer A except that m is 52.
- Example 3 A sulfonic acid group-containing segmented block polymer C was obtained in the same manner as in Example 1 using 42.27 g of hydrophilic oligomer A, 18.62 g of hydrophobic oligomer B, 0.46 g of sodium carbonate, and 350 mL of NMP. The logarithmic viscosity of Polymer C was 3.2 dL / g. A proton exchange membrane C was obtained from the obtained polymer by the above method. The chemical structure of polymer C is the same as polymer A except that n is 37.
- Example 4 A sulfonic acid group-containing segmented block polymer D was obtained in the same manner as in Example 1 using 42.27 g of hydrophilic oligomer C, 22.75 g of hydrophobic oligomer B, 0.56 g of sodium carbonate, and 370 mL of NMP. The logarithmic viscosity of Polymer D was 2.5 dL / g. A proton exchange membrane D was obtained from the obtained polymer by the above method. The methanol permeability coefficient of the proton exchange membrane D was 0.016 (mmol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ). The chemical structure of polymer D is shown below.
- Example 5 A sulfonic acid group-containing segmented block polymer E was obtained in the same manner as in Example 1 using 42.27 g of hydrophilic oligomer D, 24.29 g of hydrophobic oligomer C, 0.48 g of sodium carbonate, and 380 mL of NMP. The logarithmic viscosity of Polymer E was 2.1 dL / g. A proton exchange membrane E was obtained from the obtained polymer by the above method. The chemical structure of polymer E is shown below.
- Example 6 Using 43.00 g of hydrophilic oligomer A, 23.97 g of hydrophobic oligomer D, 0.47 g of sodium carbonate, and 380 mL of NMP, a sulfonate group-containing segmented block polymer F was obtained in the same manner as in Example 1. The logarithmic viscosity of Polymer F was 3.1 dL / g. A proton exchange membrane F was obtained from the obtained polymer by the above method. The chemical structure of polymer F is shown below.
- Example 7 A sulfonic acid group-containing segmented block polymer M was obtained in the same manner as in Example 1 using 39.58 g of the hydrophilic oligomer E, 23.97 g of the hydrophobic oligomer D, 0.47 g of sodium carbonate, and 380 mL of NMP. The logarithmic viscosity of Polymer M was 2.1 dL / g. A proton exchange membrane M was obtained from the obtained polymer by the above method. The chemical structure of polymer M is shown below.
- Example 8> Using 22.00 g of hydrophilic oligomer H, 32.75 g of hydrophobic oligomer H, 1.56 g of sodium carbonate, and 390 mL of NMP, a sulfonate group-containing segmented block polymer K was obtained in the same manner as in Example 1. The logarithmic viscosity of the polymer K was 2.4 dL / g. A proton exchange membrane K was obtained from the obtained polymer by the above method. The methanol permeability coefficient of the proton exchange membrane D was 0.004 (mmol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ). The chemical structure of polymer K is the same as polymer A except that m is 7 and n is 18.5.
- Example 9 Using 25.00 g of hydrophilic oligomer I, 14.05 g of hydrophobic oligomer A, 0.28 g of sodium carbonate, and 270 mL of NMP, a sulfonate group-containing segmented block polymer L was obtained in the same manner as in Example 1. The logarithmic viscosity of the polymer L was 2.1 dL / g. A proton exchange membrane L was obtained from the obtained polymer by the above method. The chemical structure of polymer L is shown below.
- Example 10 A sulfonic acid group-containing segmented block polymer N was obtained in the same manner as in Example 1 using 37.15 g of hydrophilic oligomer A, 19.58 g of hydrophobic oligomer I, 0.50 g of sodium carbonate, and 340 mL of NMP. The logarithmic viscosity of polymer N was 2.8 dL / g. A proton exchange membrane N was obtained from the obtained polymer by the above method. The chemical structure of polymer N is shown below.
- a proton exchange membrane O was obtained from the polymer A by a production method B of a proton exchange membrane.
- a sulfonic acid group-containing segmented block polymer G was obtained in the same manner as in Example 1 using 44.06 g of hydrophilic oligomer F, 23.89 g of hydrophobic oligomer E, 0.47 g of sodium carbonate, and 380 mL of NMP. The logarithmic viscosity of polymer G was 1.5 dL / g.
- a proton exchange membrane G was obtained from the obtained polymer by the same method as in the Example except that the reaction temperature was 160 ° C. and the reaction time was 60 hours. The chemical structure of polymer G is shown below.
- a sulfonic acid group-containing segmented block polymer H was obtained in the same manner as in Example 1 using 44.06 g of hydrophilic oligomer F, 25.38 g of hydrophobic oligomer F, 0.47 g of sodium carbonate, and 380 mL of NMP.
- the logarithmic viscosity of polymer H was 2.5 dL / g.
- a proton exchange membrane H was obtained from the obtained polymer by the above method.
- the chemical structure of polymer H is shown below.
- a sulfonic acid group-containing segmented block polymer I was obtained in the same manner as in Example 1 using 42.74 g of hydrophilic oligomer G, 25.38 g of hydrophobic oligomer F, 0.47 g of sodium carbonate, and 380 mL of NMP.
- the logarithmic viscosity of Polymer I was 1.9 dL / g.
- a proton exchange membrane I was obtained from the obtained polymer by the above method. The chemical structure of polymer I is shown below.
- a sulfonic acid group-containing segmented block polymer J was obtained in the same manner as in Example 1 using 44.06 g of hydrophilic oligomer F, 23.87 g of hydrophobic oligomer G, 0.47 g of sodium carbonate, and 380 mL of NMP.
- the logarithmic viscosity of polymer J was 1.3 dL / g.
- a proton exchange membrane J was obtained from the obtained polymer by the above method. The chemical structure of polymer J is shown below.
- Table 1 and Table 2 show the evaluation results of the proton exchange membranes obtained in Examples and Comparative Examples.
- Example 12 Addition of fibrous filler> 5 weight of potassium hexatitanate fiber (trade name: Tismo N, average fiber diameter 0.3 to 0.6 ⁇ m, average fiber length 10 to 20 ⁇ m, manufactured by Otsuka Chemical Co., Ltd.) with respect to the polymer obtained in Synthesis Example 1.
- a proton exchange membrane was obtained in the same manner as in Example 1, except that% was added.
- the proton conductivity and water absorption of the obtained membrane were the same as in Example 1, but the area swelling rate was as small as 7%, and the swelling property was improved.
- Example 13 Power generation evaluation of direct methanol fuel cell (DMFC) of proton exchange membrane D produced in Example 4> After adding a small amount of ultrapure water and isopropyl alcohol to a Pt / Ru catalyst-supporting carbon (Tanaka Kikinzoku Kogyo Co., Ltd. TEC61E54) and moistening, a 20% Nafion (registered trademark) solution (product number: SE-20192) manufactured by DuPont is used. The Pt / Ru catalyst-carrying carbon and Nafion were added at a weight ratio of 2.5: 1. Next, stirring was performed to prepare an anode catalyst paste.
- DMFC direct methanol fuel cell
- This catalyst paste was applied to Toray carbon paper TGPH-060 serving as a gas diffusion layer by screen printing so that the amount of platinum deposited was 2 mg / cm 2, and carbon paper with an electrode catalyst layer for anode was produced. . Further, after adding a small amount of ultrapure water and isopropyl alcohol to a Pt catalyst-supporting carbon (Tanaka Kikinzoku Kogyo Co., Ltd. TEC10V40E) and moistening, a 20% Nafion (registered trademark) solution (product number: SE-20192) manufactured by DuPont is used. Then, the Pt catalyst-carrying carbon and Nafion were added in a weight ratio of 2.5: 1 and stirred to prepare a cathode catalyst paste.
- a Pt catalyst-supporting carbon Teanaka Kikinzoku Kogyo Co., Ltd. TEC10V40E
- a 20% Nafion (registered trademark) solution product number: SE-20192
- This catalyst paste was applied to a Toray carbon paper TGPH-060 that had been subjected to water repellent finish and dried so that the amount of platinum deposited was 1 mg / cm 2 , thereby producing a carbon paper with an electrode catalyst layer for cathode.
- a membrane sample is sandwiched between the above two types of carbon paper with an electrode catalyst layer so that the electrode catalyst layer is in contact with the membrane sample, and pressurized and heated at 200 ° C. and 6 MPa for 3 minutes by a hot press method.
- the body was made.
- This joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and a power generation test was performed using a fuel cell power generation tester (manufactured by Toyo Corporation).
- a proton exchange membrane Nafion (trade name) 117 manufactured by DuPont was used and the press temperature was 150 ° C.
- Nafion (trade name) 117 had a methanol permeability coefficient of 0.69 (mmol ⁇ m ⁇ 1 ⁇ sec ⁇ 1 ). Where the current density was measured output voltage at 0.2 A / cm 2, the output voltage is only 0.19 V, was inferior as compared with Example 12.
- Example 14 Power generation evaluation of a fuel cell (PEFC) using hydrogen as a fuel using the proton exchange membrane of Example 1> It becomes uniform after adding commercially available 40% Pt catalyst-supported carbon (Tanaka Kikinzoku Kogyo Co., Ltd. Fuel Cell Catalyst TEC10V40E), a small amount of ultrapure water and isopropanol to a DuPont 20% Nafion (trade name) solution. To prepare a catalyst paste. This catalyst paste was uniformly applied to Toray carbon paper TGPH-060 so that the amount of platinum deposited was 0.5 mg / cm 2 and dried to prepare a gas diffusion layer with an electrode catalyst layer.
- Pt catalyst-supported carbon Teanaka Kikinzoku Kogyo Co., Ltd. Fuel Cell Catalyst TEC10V40E
- a membrane electrode assembly was obtained.
- the joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and the hydrogen generation and air humidified at 75 ° C. were supplied to the anode and the cathode at a cell temperature of 80 ° C., and the power generation characteristics were evaluated.
- the output voltage at a current density of 0.5 A / cm 2 immediately after the start was taken as the initial output.
- the reaction solution was cooled to room temperature, poured into 3000 mL of pure water to solidify the oligomer, and further washed with pure water three times to remove NMP and inorganic salts.
- the oligomer washed with water was separated by filtration and then dried under reduced pressure at 120 ° C. for 16 hours to obtain a hydrophobic oligomer J (Chemical Formula 47).
- the number average molecular weight determined by 1 H-NMR measurement was 10572.
- S-DCDPS 4,4′-dichlorodiphenylsulfone-3,3′-sodium disulfonate
- hydrophilic oligomer N > 200.0 g (407.1 mmol) of S-DCDPS, 77.7 g (416.8 mmol) of BP, 63.37 g (458.5 mmol) of potassium carbonate, and 720 mL of NMP were attached with a nitrogen introduction tube, a stirring blade, a Dean-Stark trap, and a thermometer.
- hydrophilic oligomer N was obtained in the same manner as in Synthesis Example 17 (Chemical Formula 51). The number average molecular weight determined by 1 H-NMR measurement was 20920.
- hydrophilic oligomer O > 30.0 g (61.1 mmol) of S-DCDPS, 17.96 g (96.3 mmol) of BP, 5.67 (32.9 mmol) of DCBN, 14.65 g (106.0 mmol) of potassium carbonate, and 140 mL of NMP were added to a nitrogen introduction tube, a stirring blade, In a 200 mL branch flask equipped with a Dean-Stark trap and thermometer, hydrophilic oligomer O was obtained in the same manner as in Synthesis Example 17 (Chemical Formula 52). The number average molecular weight determined by 1 H-NMR measurement was 19988.
- Example 15 7.00 g of hydrophilic oligomer M, 4.53 g of hydrophobic oligomer J, and 110 mL of NMP were placed in a 200 mL branch flask equipped with a nitrogen introduction tube, a stirring blade, a Dean-Stark trap and a thermometer, and an oil bath at 70 ° C. under a nitrogen stream. Stir in to dissolve. Thereafter, 0.24 g of decafluorobiphenyl (DFB) and 0.11 g of potassium carbonate were added, heated to 110 ° C., and reacted for 10 hours. The solid content concentration of the reaction solution was 10% by weight.
- DFB decafluorobiphenyl
- Example 16> Using the hydrophilic oligomer M 7.00 g, the hydrophobic oligomer K 4.95 g, potassium carbonate 0.12 g, DFB 0.27 g, and NMP 110 mL, the sulfonate group-containing segmented block polymer L was obtained in the same manner as in Example 1. (Chemical Formula 55). The logarithmic viscosity of the polymer L was 3.4 dL / g. A proton exchange membrane L was obtained from the obtained polymer by the above method. The chemical structure of the polymer L is the same as that of the polymer K except that the degree of polymerization of the oligomer is different.
- Example 17 Using a hydrophilic oligomer N 7.00 g, a hydrophobic oligomer J 4.5 g, potassium carbonate 0.12 g, DFB 0.22 g, and NMP 111 mL, a sulfonate group-containing segmented block polymer M was obtained in the same manner as in Example 14. (Chemical Formula 56). The logarithmic viscosity of Polymer M was 2.9 dL / g. A proton exchange membrane M was obtained from the obtained polymer by the above method. The chemical structure of polymer M is the same as polymer K except that the degree of polymerization of the oligomers is different.
- Example 18 Using a hydrophilic oligomer N 7.00 g, a hydrophobic oligomer K 4.47 g, potassium carbonate 0.11 g, DFB 0.24 g, and NMP 110 mL, a sulfonate group-containing segmented block polymer N was obtained in the same manner as in Example 14. (Chemical Formula 57). The logarithmic viscosity of polymer N was 2.7 dL / g. A proton exchange membrane N was obtained from the obtained polymer by the above method. The chemical structure of polymer N is the same as that of polymer K except that the degree of polymerization of the oligomers is different.
- Example 19 Using hydrophilic oligomer M 7.00 g, hydrophobic oligomer J 4.53 g, potassium carbonate 0.11 g, hexafluorobenzene (HB) 0.13 g, NMP 110 mL, and in the same manner as in Example 14, sulfonic acid group-containing segmentation Block polymer O was obtained (Chemical Formula 58). The logarithmic viscosity of Polymer E was 2.9 dL / g. A proton exchange membrane O was obtained from the obtained polymer by the above method. The chemical structure of polymer O is the same as polymer K except that HB is used as the chain extender.
- Example 20> Using a hydrophilic oligomer O 7.00 g, a hydrophobic oligomer J 4.47 g, potassium carbonate 0.12 g, DFB 0.26 g, and NMP 110 mL, a sulfonic acid group-containing segmented block polymer P was obtained in the same manner as in Example 14. (Chemical Formula 59). The logarithmic viscosity of the polymer P was 3.4 dL / g. A proton exchange membrane P was obtained from the obtained polymer by the above method. The chemical structure of the polymer P includes a benzonitrile structure in the hydrophilic segment as a random structure.
- Example 21 In the same manner as in Example 14, using 7.00 g of hydrophilic oligomer P, 4.91 g of hydrophobic oligomer L, 0.10 g of potassium carbonate, 0.26 g of DFB, and 110 mL of NMP, a sulfonate group-containing segmented block polymer Q was obtained. (Chemical Formula 60). The logarithmic viscosity of polymer Q was 2.5 dL / g. A proton exchange membrane Q was obtained from the obtained polymer by the above method.
- Example 22 Hydrophobic oligomer M was polymerized so that NMP was 317 ml at the same charging ratio as in Synthesis Example 14. Further, hydrophilic oligomer Q was polymerized so that NMP was 200 ml at the same charging ratio as in Synthesis Example 17. Each polymerization solution was mixed and stirred for 1 hour. Thereafter, 1.68 g of DFB was added, heated to 110 ° C., and reacted for 10 hours. Purification was performed in the same manner as in Example 14 to obtain a sulfonic acid group-containing segmented block polymer R (Chemical Formula 61). The logarithmic viscosity of Polymer R was 3.5 dL / g. A proton exchange membrane R was obtained from the obtained polymer by the above method.
- the logarithmic viscosity of the polymer S was 1.5 dL / g.
- a proton exchange membrane S was obtained from the obtained polymer by the same method as in Example, except that the reaction temperature was 160 ° C. and the reaction time was 60 hours.
- Hydrophobic oligomer N was synthesized in the same manner as in Synthesis Example 14 except that the monomer used was changed from DCBN to 4,4′-dichlorodiphenylsulfone (DCDPS) and the charge was changed (Chemical Formula 64).
- the hydrophobic oligomer N had a number average molecular weight of 13560.
- a sulfonic acid group-containing segmented block polymer T was obtained in the same manner as in Example 14 except that the charged oligomer and the hydrophobic oligomer used were changed from J to N and the hydrophilic oligomer was changed from M to Q (Chemical Formula 65).
- the logarithmic viscosity of the polymer T was 2.3 dL / g.
- a proton exchange membrane T was obtained from the obtained polymer by the same method as in the example.
- Table 3 shows the evaluation results of the proton exchange membranes obtained in the examples and comparative examples.
- Example 23 Power generation evaluation of a fuel cell (PEFC) using hydrogen as a fuel using the proton exchange membrane of Example 17> It becomes uniform after adding commercially available 40% Pt catalyst-supported carbon (Tanaka Kikinzoku Kogyo Co., Ltd. Fuel Cell Catalyst TEC10V40E), a small amount of ultrapure water and isopropanol to a DuPont 20% Nafion (trade name) solution. To prepare a catalyst paste. This catalyst paste was uniformly applied to carbon paper TGPH-060 manufactured by Toray Industries, Inc. and dried so that the amount of platinum deposited was 0.5 mg / cm 2 , thereby preparing a gas diffusion layer with an electrode catalyst layer.
- Pt catalyst-supported carbon Teanaka Kikinzoku Kogyo Co., Ltd. Fuel Cell Catalyst TEC10V40E
- a membrane electrode assembly was obtained.
- the joined body was incorporated into an evaluation fuel cell FC25-02SP manufactured by Electrochem, and the hydrogen generation and air humidified at 75 ° C. were supplied to the anode and the cathode at a cell temperature of 80 ° C., and the power generation characteristics were evaluated.
- the output voltage at a current density of 0.5 A / cm 2 immediately after the start was taken as the initial output.
- the proton exchange membrane of the present invention is a proton exchange membrane having a smaller area swelling and excellent dimensional stability, although it exhibits proton conductivity equivalent to or higher than that of a comparative example proton exchange membrane having a different structure. I understand that there is. This is considered to be derived from the benzonitrile structure of the polymer constituting the proton exchange membrane of the present invention.
- the sulfonic acid group-containing segmented block polymer of the present invention can be used as a proton exchange membrane for a fuel cell that can exhibit high output and high durability, and greatly contributes to industrial development.
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Abstract
Description
また、末端修飾などを行わず、より簡便な手法として各セグメントの末端基を同じにしておいて、フッ素などのハロゲン元素を含む芳香族系鎖延長剤を用いて両オリゴマーを反応させるブロック共重合ポリマーの合成が非特許文献3に報告されている。
これらのポリマーでは、ハロゲン元素を含む構成単位は、異種のセグメント間の結合部分にのみ存在するため、分子中のハロゲン量が少なくなるという利点がある。しかしながら、セグメント構造、特にスルホン酸基を実質的に有さない疎水性セグメントの構造によっては、膨潤性が高いものがあり、燃料電池に用いた場合の耐久性に問題がある場合があった。
すなわち、本願第1の発明は、
(1) 分子中にそれぞれ一つ以上の親水性セグメントと疎水性セグメントを有するブロック共重合ポリマーであって、下記化学式1で表される構造であり、N-メチル-2-ピロリドンを溶媒とした0.5g/dLの溶液について30℃で測定される対数粘度が、0.5~5.0dL/gの範囲であることを特徴とするブロック共重合ポリマー。
(13)親水性オリゴマー、疎水性オリゴマーおよび鎖延長剤を反応させてブロック共重合体ポリマーを合成する方法において、
疎水性オリゴマーが下記化学式7
(式中、Zはそれぞれ独立してO又はS原子のいずれかを、Ar1は2価の芳香族基を、nは2~100の整数を、それぞれ表す。)
で表される構造を分子中に含んでおり、親水性オリゴマーが下記化学式8
(式中、XはH又は1価の陽イオンを、Yはスルホニル基、又はカルボニル基を、ZはO
又はS原子のいずれかを、Ar2は、2価の芳香族基を、mは2~100の整数を、それ
ぞれ表す。)
で表される構造を分子中に含むことを特徴とするブロック共重合ポリマーの合成法。
本願第1の発明のスルホン酸基含有セグメント化ブロック共重合ポリマーは、分子中にそれぞれ一つ以上の親水性セグメントと疎水性セグメントを有するブロック共重合ポリマーであって、下記化学式1で表される構造であり、N-メチル-2-ピロリドンを溶媒とした0.5g/dLの溶液について30℃で測定される対数粘度が、0.5~5.0dL/gの範囲であることを特徴とするブロック共重合ポリマー。
から好ましい。いずれもがO原子であることがより好ましい。ただし、S原子であると耐酸化性が向上する場合がある。
本願第1の発明のスルホン酸基含有セグメント化ブロック共重合ポリマーにおける親水性オリゴマーは、下記化学式4で表されるスルホン化モノマーを各種ビスフェノール類又は各種ビスチオフェノール類と反応させて合成することができる。
本願第1の発明のスルホン酸基含有セグメント化ブロック共重合ポリマーにおける疎水性オリゴマーは、下記化学式5A又は5Bで表されるモノマーを各種ビスフェノール類又は各種ビスチオフェノール類と反応させた後、化学式6A、6B、6Cで表される化合物を反応させることによって合成することができる。
セグメント化ブロック共重合ポリマーは、上記のようにして合成した、疎水性オリゴマーと親水性オリゴマーを反応させることにより得ることができる。疎水性オリゴマー及び親水性オリゴマーは、それぞれ独立して構造、分子量、分子量分布、及び末端基の異なるオリゴマーからなる群より選ばれる1種以上のオリゴマーを用いることができる。各オリゴマーの分子量は公知の任意の方法で求めることができるが、末端基を定量して数平均分子量を求めることが好ましい。末端基の定量は、滴定法、比色法、ラベル法、NMR法、元素分析など公知の任意の方法を用いることが可能であるが、NMR法が簡便で正確性に優れるため好ましく、1H-NMR法がより好ましい。本発明のおける疎水性オリゴマーは、ベンゾニトリル構造を有することを特徴とするが、その構造ゆえに溶媒への溶解性が乏しい。よって、NMR測定の際に、適当な重水素化溶媒に溶解しない場合には、N-メチル-2-ピロリドンなど、疎水性オリゴマーが溶解する通常の溶媒に溶解した溶液に、重水素化ジメチルスルホキシドなどの重水素化溶媒を加えて測定することが好ましい。
親水性オリゴマー、疎水性オリゴマーおよび鎖延長剤を反応させてブロック共重合体ポリマーを合成する方法において、疎水性オリゴマーが下記化学式7
(式中、Zはそれぞれ独立してO又はS原子のいずれかを、Ar1は2価の芳香族基を、nは2~100の整数を、それぞれ表す。)
で表される構造を分子中に含んでおり、疎水性オリゴマーが下記化学式8
(式中、XはH又は1価の陽イオンを、Yはスルホニル基、又はカルボニル基を、ZはO
又はS原子のいずれかを、Ar2は、2価の芳香族基を、mは2~100の整数を、それ
ぞれ表す。)
で表される構造を分子中に含むことを特徴とするブロック共重合ポリマーの製造方法である。
から好ましい。いずれもがO原子であることがより好ましい。ただし、S原子であると耐酸化性が向上する場合がある。
本願第2の発明のスルホン酸基含有セグメント化ブロック共重合ポリマーにおける親水性オリゴマーは、下記化学式4で表されるスルホン化モノマーを各種ビスフェノール類又は各種ビスチオフェノール類と反応させて合成することができる。また、下記化学式4で表されるスルホン化モノマーに加えて4,4‘-ジクロロジフェニルスルホンや2,6-ジクロロベンゾニトリルのようなジハロゲン化物を用いて各種ビスフェノール類又は各種ビスチオフェノール類と反応させて合成しても良い。
本願第2の発明のスルホン酸基含有セグメント化ブロック共重合ポリマーにおける疎水性オリゴマーは、下記化学式5A又は5Bで表されるモノマーを各種ビスフェノール類又は各種ビスチオフェノール類と反応させることによって合成することができる。
セグメント化ブロック共重合ポリマーは、上記のようにして合成した疎水性オリゴマーと親水性オリゴマーを鎖延長剤と反応させることにより得ることができる。疎水性オリゴマー及び親水性オリゴマーは、それぞれ独立して構造、分子量、及び分子量分布の異なるオリゴマーからなる群より選ばれる1種以上のオリゴマーを用いることができる。各オリゴマーの分子量は公知の任意の方法で求めることができるが、末端基を定量して数平均分子量を求めることが好ましい。末端基の定量は、滴定法、比色法、ラベル法、NMR法、元素分析など公知の任意の方法を用いることが可能であるが、NMR法が簡便で正確性に優れるため好ましく、1H-NMR法がより好ましい。本発明のおける疎水性オリゴマーは、ベンゾニトリル構造を有することを特徴とするが、その構造ゆえに溶媒への溶解性が乏しい。よって、NMR測定の際に、適当な重水素化溶媒に溶解しない場合には、N-メチル-2-ピロリドンなど、疎水性オリゴマーが溶解する通常の溶媒に溶解した溶液に、重水素化ジメチルスルホキシドなどの重水素化溶媒を加えて測定することが好ましい。
(16)芳香族系鎖延長剤のハロゲンがフッ素であることを特徴とする(13)~(15)に記載のブロック共重合体ポリマーの合成法。
(17)芳香族系鎖延長剤がパーフルオロ化合物(ただし、シアノ基、スルホニル基、スルフィニル基、カルボニル基からなる群より選ばれる基を含んでいてもよい)であることを特徴とする(16)に記載のブロック共重合体ポリマーの合成法。
用いる鎖延長剤としては、ハロゲンがフッ素であると、反応性が高くセグメント長の低下などの副反応を抑制できるので、ハロゲンがフッ素である芳香族系鎖延長剤が好ましい。さらに、ハロゲンがフッ素である芳香族系鎖延長剤は、1分子中に3個以上のフッ素原子を有していることが好ましく、2個以上のフッ素原子が隣接していることがより好ましく、パーフルオロ化合物であると、より反応性が高いため好ましい。ハロゲンがフッ素である芳香族系鎖延長剤は電子吸引性を置換基として有していてもよく、電子吸引性基はフッ素原子に対してオルト位、又はパラ位であると好ましい。電子吸引性基の例としては、シアノ基、スルホニル基、スルフィニル基、カルボニル基などを挙げることができるが、これらに限定されるものではない。ハロゲンがフッ素である芳香族系鎖延長剤の好ましい例としては、単数の芳香族環(電子吸引性基を置換基として有していてもよい)、あるいは複数の芳香族基が電子吸引性基で連結された芳香族環が、パーフルオロ化された化合物を挙げることができ、より具体的には、ヘキサフルオロベンゼン、デカフルオロビフェニル、デカフルオロベンゾフェノン、デカフルオロジフェニルスルホン、ペンタフルオロベンゾニトリルのいずれか、またはこれらの混合物を挙げることができる。また、ヘキサフルオロベンゼン、デカフルオロビフェニル、デカフルオロベンゾフェノン、デカフルオロジフェニルスルホン、ペンタフルオロベンゾニトリルなどの化合物において、フッ素原子の一部が、置換された化合物も、上記の要件を満たす範囲で用いることができる。フッ素原子を置換するものとしては、水素原子や、塩素、臭素、ヨウ素などの他のハロゲン原子、フェノキシ基、フェニル基、メチル基などの炭化水素基などが例として挙げられる、これらに限定されるものではない。
ポリマー粉末を0.5g/dLの濃度でN-メチル-2-ピロリドンに溶解し、30℃の恒温槽中でウベローデ型粘度計を用いて粘度測定を行い、対数粘度(ln[ta/tb])/cで評価した(taは試料溶液の落下秒数、tbは溶媒のみの落下秒数、cはポリマー濃度を表す)。
乾燥したプロトン交換膜100mgを、0.01NのNaOH水溶液50mlに浸漬し、25℃で一晩攪拌した。その後、0.05NのHCl水溶液で中和滴定した。中和滴定には、平沼産業(株)製、電位差滴定装置COMTITE-980を用いた。イオン交換当量は下記式で計算して求めた。
イオン交換容量[meq/g]=(10-滴定量[ml])/2
自作測定用プローブ(テフロン(登録商標)製)上で短冊状膜試料の表面に白金線(直径:0.2mm)を押しあて、80℃95%RHの恒温・恒湿オーブン(株式会社ナガノ科学機械製作所、LH-20-01)中に試料を保持し、白金線間のインピーダンスをSOLARTRON社1250FREQUENCY RESPONSE ANALYSERにより測定した。極間距離を変化させて測定し、極間距離とC-Cプロットから見積もられる抵抗測定値をプロットした勾配から以下の式により膜と白金線間の接触抵抗をキャンセルした導電率を算出した。
導電率[S/cm]=1/膜幅[cm]×膜厚[cm]×抵抗極間勾配[Ω/cm]
ポリマー(スルホン酸基はNaもしくはK塩)を溶媒に溶解し、VARIAN社製UNITY-500を用いて1H-NMRは室温で、13C-NMRは70℃でそれぞれ測定を行った。溶媒にはN-メチル-2-ピロリドンと重ジメチルスルホキシドの混合溶媒(85/15 vol./vol.)を用いた。親水性セグメント及び疎水性セグメントをそれぞれ構成する親水性オリゴマー及び疎水性オリゴマーは、1H-NMRスペクトルを測定し、末端基由来のピークと骨格部分のピークのそれぞれの積分比から、数平均分子量を求めた。例えば、下記の合成例1の疎水性オリゴマーAで例示すると、ビフェニル構造におけるエーテル結合のオルト位のプロトンのピークは、末端基由来(パーフルオロビフェニルに結合した箇所)のものは7.2ppmに検出され、骨格中のものは7.3ppmに検出されるので、これらのピークの積分比から数平均分子量を求めた。また、下記の合成例5の親水性オリゴマーAで例示すると、ビフェニル構造におけるエーテル結合のオルト位のプロトンのピークは、末端基由来(フェノール性水酸基のオルト位)のものは6.8ppmに、骨格中のものは7.3ppmに、それぞれ検出されるので、これらのピークの積分比から数平均分子量を求めた。また、ブロックポリマーについては、親水性セグメントと疎水性セグメントの組成比を1H-NMRで、セグメント長の低下の有無の確認を13C-NMRで、それぞれ分析した。ブロックポリマーの合成において、副反応で各セグメントの分子量が低下した場合、セグメント間の交換反応に由来するピークが13C-NMRによって検出される。例えば、下記比較例1の構造のブロックポリマーでは、交換反応由来のピークは155.5ppm及び157.0ppmに現れたのに対して、ほぼ同様の構造の下記実施例1のブロックポリマーでは、それらのピークは痕跡程度で明確に確認できなかった。このようにして13C-NMRによって、各オリゴマー由来のセグメント連鎖長が保持されているかどうかを確認した。さらに、下記実施例に記載の他のブロックポリマーにおいても実施例1のブロックポリマーと同様に交換由来のピークを明確に確認できなかった。実施例19のブロックポリマーにおいては、はじめから交換由来のものと同じピーク示す構造を含むためはっきりと交換の確認ができていない。
23℃50%RHの室内に1日放置しておいたプロトン交換膜を50mm四方に切り出した後、80℃の熱水に24時間浸漬した。浸漬後、膜の寸法及び重量をすばやく測定した。膜は120℃で3時間乾燥させ、乾燥重量を測定した。以下の式に従って、吸水率及び面積膨潤率を算出した。膜の寸法は特定の頂点に結合した直交する2辺の長さを測定した。
吸水率(%)={浸漬後の重量(g)-乾燥重量(g)}÷乾燥重量(g)×100
面積膨潤率(%)={浸漬後の辺の長さA(mm)×浸漬後の辺の長さB(mm)}÷{50×50}×100-100
25℃の室内において、二つのガラス水槽を、サンプルを隔膜として連結し、片方の水槽に5Mのメタノール水溶液、もう片方に蒸留水をそれぞれ入れ、蒸留水を入れた側のメタノール濃度を適当な時間ごとに定量した。メタノールの定量はガスクロマトグラフィー法で行い、あらかじめ所定の濃度のメタノール溶液を注入したときのピーク面積から作成した検量線を用いてメタノール濃度を算出した。得られたメタノール濃度を経過時間に対してプロットしたときの傾きから、以下の式によりメタノール透過係数を求めた。
メタノール透過係数(mmol・m-1・sec-1)=プロットの傾き(mmol・sec-1)÷膜面積(m2)×膜厚(m)
ポリマー(スルホン酸基が塩型のもの)2.0gをN-メチル-2-ピロリドン(略号:NMP)18mLに溶解し、アプリケーターを用いてガラス板上に500μmの厚みでキャストし、100℃で1時間、150℃で1時間加熱して乾燥した。その後、ガラス板を室温付近まで放冷し、膜ごと水につけて膜を剥離した。剥離した膜は純水に浸漬した後、1N硫酸に1時間浸漬して、スルホン酸基を酸型に変換し、純水で洗浄して遊離の硫酸を除き、風乾してプロトン交換膜を得た。
ポリマー(スルホン酸基が塩型のもの)20.0gをN-メチル-2-ピロリドン(略号:NMP)180mLに溶解し、加圧濾過した後、厚み190μmのポリエチレンテレフタレート製のフィルム上に400μmの厚みで連続的にキャストし、130℃で30分間加熱して乾燥して得られた膜をポリエチレンテレフタレート製のフィルムと共に巻き取った。得られた膜はポリエチレンテレフタレート製のフィルムに付着した状態で、連続的に純水に浸漬させた後、連続的に1mol/Lの硫酸水溶液に30分間浸漬させて、スルホン酸基を酸型に変換し、純水で洗浄して遊離の硫酸を除いた後、乾燥し、ポリエチレンテレフタレート製のフィルムから剥離してプロトン交換膜を得た。
2,6-ジクロロベンゾニトリル(略号:DCBN)49.97g(290.5mmol)、4,4’-ビフェノール(略号:BP)54.99g(295.3mmol)、炭酸カリウム46.94g(339.6mmol)、NMP750mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。トルエンとの共沸による脱水を140℃で行なった後、トルエンをすべて留去した。その後、200℃に昇温し、15時間加熱した。窒素導入管、攪拌翼、冷却還流管、温度計を取り付けた別の1000mL枝付きフラスコに、NMP200mLとパーフルオロビフェニル4.85gを入れ、窒素気流下、攪拌しながら、オイルバス中で110℃に加熱した。そこに、DCBNとBPの反応溶液を、滴下漏斗を用いて2時間かけて攪拌しながら投入し、投入完了後、さらに2時間攪拌した。反応溶液を室温まで冷却した後、3000mLの純水に注ぎオリゴマーを固化させ、さらに純水で3回洗浄して、NMP及び無機塩を除去した。水洗したオリゴマーは、濾別した後、100℃で2時間乾燥させた後、室温まで冷却し、3000mLのアセトンで2回洗浄し、過剰のパーフルオロビフェニルを除去した。再びオリゴマーを濾別し、120℃で16時間減圧乾燥して疎水性オリゴマーAを得た。1H-NMR測定による数平均分子量は13880だった。疎水性オリゴマーAの化学構造を以下に示す。
DCBN49.97g(290.5mmol)、BP54.99g(295.3mmol)、炭酸カリウム46.94g(339.6mmol)、NMP770mL、トルエン130mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。トルエンとの共沸による脱水を140℃で行なった後、トルエンをすべて留去した。その後、200℃に昇温し、15時間加熱した。窒素導入管、攪拌翼、冷却還流管、温度計を取り付けた別の1000mL枝付きフラスコに、NMP200mLとパーフルオロビフェニル8.09gを入れ、窒素気流下、攪拌しながら、オイルバス中で110℃に加熱した。そこに、DCBNとBPの反応溶液を、滴下漏斗を用いて2時間かけて攪拌しながら投入し、投入完了後、さらに3時間攪拌した。反応溶液を室温まで冷却した後、3000mLのアセトンに注ぎオリゴマーを固化させた。細かい沈殿を含む上澄みは除去し、さらにアセトンで2回洗浄した後、純水で3回洗浄して、NMP及び無機塩を除去した。その後、オリゴマーを濾別し、120℃で16時間減圧乾燥して疎水性オリゴマーBを得た。1H-NMR測定による数平均分子量は11260だった。疎水性オリゴマーBの化学構造を以下に示す。
パーフルオロビフェニル4.85gの代わりに、パーフルオロジフェニルスルホン5.78gを用いた他は合成例1と同様にして疎水性オリゴマーCを合成した。1H-NMR測定による数平均分子量は14010であった。疎水性オリゴマーCの化学構造を以下に示す。
DCBN29.49g(171.5mmol)、2,2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパン(略号:BFP)59.35g(176.5mmol)、炭酸カリウム28.06g(203.0mmol)、NMP700mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、合成例1と同様の操作によって疎水性オリゴマーDを得た。1H-NMR測定による数平均分子量は14250だった。疎水性オリゴマーDの化学構造を以下に示す。
DCBN49.97g(290.5mmol)、BP57.02g(306.2mmol)、炭酸カリウム46.55g(336.8mmol)、NMP770mL、トルエン130mLを窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。トルエンとの共沸による脱水を140℃で行なった後、トルエンをすべて留去した。その後、200℃に昇温し、15時間加熱した。窒素導入管、攪拌翼、冷却還流管、温度計を取り付けた別の1000mL枝付きフラスコに、NMP200mLとパーフルオロビフェニル30.09gを入れ、窒素気流下、攪拌しながら、オイルバス中で110℃に加熱した。そこに、DCBNとBPの反応溶液を、滴下漏斗を用いて2時間かけて攪拌しながら投入し、投入完了後、さらに3時間攪拌した。反応溶液を室温まで冷却した後、3000mLのアセトンに注ぎオリゴマーを固化させた。細かい沈殿を含む上澄みは除去し、さらにアセトンで2回洗浄した後、純水で3回洗浄して、NMP及び無機塩を除去した。その後、オリゴマーを濾別し、120℃で16時間減圧乾燥して疎水性オリゴマーEを得た。1H-NMR測定による数平均分子量は5810だった。疎水性オリゴマーHの化学構造を以下に示す。
パーフルオロビフェニル4.85gの代わりに、パーフルオロベンゾフェノン5.26gを用いた他は合成例1と同様にして疎水性オリゴマーIを合成した。1H-NMR測定による数平均分子量は13050であった。疎水性オリゴマーIの化学構造を以下に示す。
4,4’-ジクロロジフェニルスルホン-3,3’-ジスルホン酸ソーダ(略号:S-DCDPS)250.0g(508.9mmol)、BP97.04g(520.7mmol)、炭酸ナトリウム66.23g(624.9mmol)、NMP650mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。トルエンとの共沸による脱水を140℃で行なった後、トルエンをすべて留去した。その後、200℃に昇温し、16時間加熱した。続いて、NMP500mLを投入し、攪拌しながら室温まで冷却した。得られた溶液を、25G2ガラスフィルターで吸引濾過したところ、黄色の透明な溶液が得られた。得られた溶液を3Lのアセトンに滴下してオリゴマーを固化させた。オリゴマーはさらにアセトンで3回洗浄した後、濾別して減圧乾燥し親水性オリゴマーAを得た。1H-NMR測定による数平均分子量は25560であった。親水性オリゴマーAの化学構造を以下に示す。
S-DCDPS250.0g(508.9mmol)、BP96.62g(518.5mmol)、炭酸ナトリウム65.95g(622.2mmol)、NMP650mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーBを得た。1H-NMR測定による数平均分子量は31340であった。親水性オリゴマーBの化学構造を以下に示す。
S-DCDPS250.0g(508.9mmol)、BP97.46g(523.0mmol)、炭酸ナトリウム66.52g(627.7mmol)、NMP650mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーCを得た。1H-NMR測定による数平均分子量は20920であった。親水性オリゴマーCの化学構造を以下に示す。
S-DCDPS250.0g(508.9mmol)、BFP175.09g(523.0mmol)、炭酸ナトリウム66.23g(624.9mmol)、NMP800mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーDを得た。1H-NMR測定による数平均分子量は24380であった。親水性オリゴマーDの化学構造を以下に示す。
4,4’-ジクロロベンゾフェノン-3,3-ジスルホン酸ナトリウム231.7g(508.9mmol)、BP97.04g(520.7mmol)、炭酸ナトリウム66.23g(624.9mmol)、NMP800mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーEを得た。1H-NMR測定による数平均分子量は23530であった。親水性オリゴマーEの化学構造を以下に示す。
S-DCDPS250.0g(508.9mmol)、BP106.18g(570.2mmol)、炭酸ナトリウム69.50g(655.8mmol)、NMP650mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーHを得た。1H-NMR測定による数平均分子量は3890であった。親水性オリゴマーHの化学構造を以下に示す。
S-DCDPS250.0g(508.9mmol)、1,3-ビス(4-ヒドロキシフェニル)アダマンタン167.72g(523.5mmol)、炭酸ナトリウム63.80g(602.0mmol)、NMP650mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例6と同様にして親水性オリゴマーIを得た。1H-NMR測定による数平均分子量は24700であった。親水性オリゴマーIの化学構造を以下に示す。
親水性オリゴマーA 45.00g、疎水性オリゴマーA 24.61g、炭酸ナトリウム0.28g、NMP400mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、窒素気流下50℃のオイルバス中で攪拌し溶解させた。その後、110℃まで加熱し、10時間反応させた。その後、室温まで冷却し、3Lの純水中に滴下してポリマーを固化させた。純水で3回洗浄した後、純水に浸漬したまま80℃で16時間処理し、その後で純水を除いて熱水洗浄を行った。その後、熱水洗浄をもう一度繰り返した。さらに水を除去したポリマーを、1000mLのイソプロパノールと500mLの水との混合溶媒に室温で16時間浸漬し、ポリマーを取り出し洗浄を行った。同じ操作をもう一度行った。その後、濾過でポリマーを濾別し、120℃で12時間減圧乾燥してスルホン酸基含有セグメント化ブロックポリマーAを得た。ポリマーAの対数粘度は、2.1dL/gだった。得られたポリマーからプロトン交換膜の作製方法Aによってプロトン交換膜Aを得た。ポリマーAの化学構造を以下に示す。
親水性オリゴマーB 42.27g、疎水性オリゴマーA 18.72g、炭酸ナトリウム0.37g、NMP350mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーBを得た。ポリマーBの対数粘度は、2.6dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Bを得た。ポリマーBの化学構造は、mが52である他は、ポリマーAと同じである。
親水性オリゴマーA 42.27g、疎水性オリゴマーB 18.62g、炭酸ナトリウム0.46g、NMP350mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーCを得た。ポリマーCの対数粘度は、3.2dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Cを得た。ポリマーCの化学構造は、nが37である他は、ポリマーAと同じである。
親水性オリゴマーC 42.27g、疎水性オリゴマーB 22.75g、炭酸ナトリウム0.56g、NMP370mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーDを得た。ポリマーDの対数粘度は、2.5dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Dを得た。プロトン交換膜Dのメタノール透過係数は、0.016(mmol・m-1・sec-1)であった。ポリマーDの化学構造を以下に示す。
親水性オリゴマーD 42.27g、疎水性オリゴマーC 24.29g、炭酸ナトリウム0.48g、NMP380mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーEを得た。ポリマーEの対数粘度は、2.1dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Eを得た。ポリマーEの化学構造を以下に示す。
親水性オリゴマーA 43.00g、疎水性オリゴマーD 23.97g、炭酸ナトリウム0.47g、NMP380mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーFを得た。ポリマーFの対数粘度は、3.1dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Fを得た。ポリマーFの化学構造を以下に示す。
親水性オリゴマーE 39.58g、疎水性オリゴマーD 23.97g、炭酸ナトリウム0.47g、NMP380mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーMを得た。ポリマーMの対数粘度は、2.1dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Mを得た。ポリマーMの化学構造を以下に示す。
親水性オリゴマーH 22.00g、疎水性オリゴマーH 32.75g、炭酸ナトリウム1.56g、NMP390mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーKを得た。ポリマーKの対数粘度は、2.4dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Kを得た。プロトン交換膜Dのメタノール透過係数は、0.004(mmol・m-1・sec-1)であった。ポリマーKの化学構造は、mが7、nが18.5である他は、ポリマーAと同じである。
親水性オリゴマーI 25.00g、疎水性オリゴマーA 14.05g、炭酸ナトリウム0.28g、NMP270mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーLを得た。ポリマーLの対数粘度は、2.1dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Lを得た。ポリマーLの化学構造を以下に示す。
親水性オリゴマーA 37.15g、疎水性オリゴマーI 19.58g、炭酸ナトリウム0.50g、NMP340mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーNを得た。ポリマーNの対数粘度は、2.8dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Nを得た。ポリマーNの化学構造を以下に示す。
ポリマーAからプロトン交換膜の作製方法Bによってプロトン交換膜Oを得た。
用いる原料や仕込み量を変えた他は、上記合成例と同様にして、下記構造の疎水性オリゴマーE及び親水性オリゴマーFをそれぞれ合成した。
用いる原料や仕込み量を変えた他は、上記合成例と同様にして、下記構造の疎水性オリゴマーFを合成した。
用いる原料や仕込み量を変えた他は、上記合成例と同様にして、下記構造の親水性オリゴマーGを合成した。
用いる原料や仕込み量を変えた他は、上記合成例と同様にして、下記構造の疎水性オリゴマーGを合成した。
合成例1で得られたポリマーに対して、六チタン酸カリウム繊維(大塚化学株式会社製
商品名:ティスモN、平均繊維径 0.3~0.6μm、平均繊維長10~20μm)を5重量%加えたほかは、実施例1と同様にしてプロトン交換膜を得た。得られた膜のプロトン伝導性と吸水率は、実施例1と同等であったが、面積膨潤率は7%と小さくなり、膨潤性が改良されていた。
Pt/Ru触媒担持カーボン(田中貴金属工業株式会社TEC61E54)に少量の超純水及びイソプロピルアルコールを加えて湿らせた後、デュポン社製20%ナフィオン(登録商標)溶液(品番:SE-20192)を、Pt/Ru触媒担持カーボンとナフィオンの重量比が2.5:1になるように加えた。次いで撹拌してアノード用触媒ペーストを調製した。この触媒ペーストを、ガス拡散層となる東レ製カーボンペーパーTGPH-060に白金の付着量が2mg/cm2になるようにスクリーン印刷により塗布乾燥して、アノード用電極触媒層付きカーボンペーパーを作製した。また、Pt触媒担持カーボン(田中貴金属工業株式会社TEC10V40E)に少量の超純水及びイソプロピルアルコールを加えて湿らせた後、デュポン社製20%ナフィオン(登録商標)溶液(品番:SE-20192)を、Pt触媒担持カーボンとナフィオンの重量比が2.5:1となるように加え、撹拌してカソード用触媒ペーストを調製した。この触媒ペーストを、撥水加工を施した東レ製カーボンペーパーTGPH-060に白金の付着量が1mg/cm2となるように塗布・乾燥して、カソード用電極触媒層付きカーボンペーパーを作製した。上記2種類の電極触媒層付きカーボンペーパーの間に、膜試料を、電極触媒層が膜試料に接するように挟み、ホットプレス法により200℃、6MPaにて3分間加圧、加熱し膜電極接合体を作製した。この接合体をElectrochem社製評価用燃料電池セルFC25-02SPに組み込み、燃料電池発電試験機(株式会社東陽テクニカ製)を用いて発電試験を行った。発電は、セル温度70℃で、アノードに70℃に調整した1mol/Lのメタノール水溶液(1.5mL/min)を、カソードに70℃に調整した高純度空気ガス(80mL/min)を、それぞれ供給し、電流密度が0.2A/cm2における出力電圧を測定したところ、0.29Vの出力電圧を示した。
デュポン社製プロトン交換膜ナフィオン(商品名)117を用い、プレス温度を150℃にした他は、実施例13と同様にして発電評価を行った。ナフィオン(商品名)117のメタノール透過係数は、0.69(mmol・m-1・sec-1)であった。電流密度が0.2A/cm2における出力電圧を測定したところ、出力電圧は0.19Vしかなく、実施例12に比べ劣るものであった。
デュポン社製20%ナフィオン(商品名)溶液に、市販の40%Pt触媒担持カーボン(田中貴金属工業株式会社 燃料電池用触媒 TEC10V40E)と、少量の超純水及びイソプロパノールを加えた後、均一になるまで撹拌し、触媒ペーストを調製した。この触媒ペーストを、東レ製カーボンペーパーTGPH-060に白金の付着量が0.5mg/cm2になるように均一に塗布・乾燥して、電極触媒層付きガス拡散層を作製した。上記の電極触媒層付きガス拡散層の間に、高分子電解質膜を、電極触媒層が膜に接するように挟み、ホットプレス法により200℃、8MPaにて3分間加圧、加熱することにより、膜電極接合体とした。この接合体をElectrochem社製の評価用燃料電池セルFC25-02SPに組み込んでセル温度80℃で、アノード及びカソードにそれぞれ75℃で加湿した水素と空気を供給して発電特性を評価した。開始直後における電流密度が0.5A/cm2における出力電圧を初期出力とした。また、耐久性評価として、1時間に3回の割合で開回路電圧を測定しつつ上記の条件で2000時間を上限として連続運転を行った。開回路電圧が開始直後の値よりも10%以上低下したときの時間を耐久時間とした。実施例1のプロトン交換膜を用いたPEFC発電評価における初期電圧は0.71Vであり、連続運転では2000時間経過後も電圧低下は3%であった。
比較例2のプロトン交換膜を用いて実施例14と同様にPEFC発電評価を行ったところ1576時間で出力が10%低下しており、実施例14に比べ劣るものであった。
2,6-ジクロロベンゾニトリル(略号:DCBN)65.00g(376.8mmol)、4,4’-ビフェノール(略号:BP)71.62g(384.3mmol)、炭酸カリウム58.43g(422.8mmol)、NMP950mLを窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。200℃に昇温し、4時間攪拌した。反応溶液を室温まで冷却した後、3000mLの純水に注ぎオリゴマーを固化させ、さらに純水で3回洗浄して、NMP及び無機塩を除去した。水洗したオリゴマーは、濾別した後、120℃で16時間減圧乾燥して疎水性オリゴマーJを得た(化47)。1H-NMR測定による数平均分子量は10572だった。
DCBN30.00g(173.9mmol)、BP32.87g(176.4mmol)、炭酸カリウム29.25g(211.7mmol)、NMP440mLを窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、合成例14と同様の操作によって疎水性オリゴマーKを得た(化48)。1H-NMR測定による数平均分子量は12169だった。
DCBN29.49g(171.5mmol)、2,2-ビス(4-ヒドロキシフェニル)ヘキサフルオロプロパン(略号:BFP)59.35g(176.5mmol)、炭酸カリウム28.06g(203.0mmol)、NMP700mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた1000mL枝付きフラスコに入れ、合成例14と同様の操作によって疎水性オリゴマーLを得た(化49)。1H-NMR測定による数平均分子量は13620だった。
4,4’-ジクロロジフェニルスルホン-3,3’-ジスルホン酸ソーダ(略号:S-DCDPS)200.0g(407.1mmol)、BP77.41g(415.4mmol)、炭酸カリウム63.2g(457.0mmol)、NMP720mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、オイルバス中で攪拌しつつ窒素気流下で加熱した。その後、200℃に昇温し、18時間加熱した。続いて、NMP300mLを投入し、攪拌しながら室温まで冷却した。得られた溶液を、25G2ガラスフィルターで吸引濾過し、得られた溶液を3Lのアセトンに滴下してオリゴマーを固化させた。オリゴマーはさらにアセトンで3回洗浄した後、濾別して減圧乾燥し親水性オリゴマーMを得た(化50)。1H-NMR測定による数平均分子量は24361であった。
S-DCDPS200.0g(407.1mmol)、BP77.7g(416.8mmol)、炭酸カリウム63.37g(458.5mmol)、NMP720mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例17と同様にして親水性オリゴマーNを得た(化51)。1H-NMR測定による数平均分子量は20920であった。
S-DCDPS30.0g(61.1mmol)、BP17.96g(96.3mmol)、DCBN5.67(32.9mmol)、炭酸カリウム14.65g(106.0mmol)、NMP140mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた200mL枝付きフラスコに入れ、合成例17と同様にして親水性オリゴマーOを得た(化52)。1H-NMR測定による数平均分子量は19898であった。
S-DCDPS250.0g(508.9mmol)、BFP175.09g(523.0mmol)、炭酸ナトリウム66.23g(624.9mmol)、NMP800mL、トルエン150mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた2000mL枝付きフラスコに入れ、合成例4と同様にして親水性オリゴマーPを得た(化53)。1H-NMR測定による数平均分子量は24380であった。
親水性オリゴマーM 7.00g、疎水性オリゴマーJ 4.53g、NMP110mLを、窒素導入管、攪拌翼、ディーンスタークトラップ、温度計を取り付けた200mL枝付きフラスコに入れ、窒素気流下70℃のオイルバス中で攪拌し溶解させた。その後、デカフルオロビフェニル(DFB)0.24g、炭酸カリウム0.11gを加え、110℃まで加熱し、10時間反応させた。反応溶液の固形分濃度は10重量%とした。その後、室温まで冷却し、1Lの純水中に滴下してポリマーを固化させた。純水で3回洗浄した後、純水に浸漬したまま80℃で5時間処理した。さらに水を除去したポリマーを、1000mLのイソプロパノールと500mLの水との混合溶媒に室温で16時間浸漬し、ポリマーを取り出し洗浄を行った。同じ操作をもう一度行った。その後、濾過でポリマーを濾別し、120℃で12時間減圧乾燥してスルホン酸基含有セグメント化ブロックポリマーKを得た(化54)。ポリマーKの対数粘度は、3.1dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Kを得た。
親水性オリゴマーM 7.00g、疎水性オリゴマーK 4.95g、炭酸カリウム0.12g、DFB0.27g、NMP110mLを用い、実施例1と同様にして、スルホン酸基含有セグメント化ブロックポリマーLを得た(化55)。ポリマーLの対数粘度は、3.4dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Lを得た。ポリマーLの化学構造は、オリゴマーの重合度が異なる以外はポリマーKと同じである。
親水性オリゴマーN 7.00g、疎水性オリゴマーJ 4.5g、炭酸カリウム0.12g、DFB0.22g、NMP111mLを用い、実施例14と同様にして、スルホン酸基含有セグメント化ブロックポリマーMを得た(化56)。ポリマーMの対数粘度は、2.9dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Mを得た。ポリマーMの化学構造は、オリゴマーの重合度が異なる以外はポリマーKと同じである。
親水性オリゴマーN 7.00g、疎水性オリゴマーK 4.47g、炭酸カリウム0.11g、DFB0.24g、NMP110mLを用い、実施例14と同様にして、スルホン酸基含有セグメント化ブロックポリマーNを得た(化57)。ポリマーNの対数粘度は、2.7dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Nを得た。ポリマーNの化学構造は、オリゴマーの重合度が異なる以外はポリマーKと同じである。
親水性オリゴマーM 7.00g、疎水性オリゴマーJ 4.53g、炭酸カリウム0.11g、ヘキサフルオロベンゼン(HB)0.13g、 NMP110mLを用い、実施例14と同様にして、スルホン酸基含有セグメント化ブロックポリマーOを得た(化58)。ポリマーEの対数粘度は、2.9dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Oを得た。ポリマーOの化学構造は、鎖延長剤としてHBを使用した以外はポリマーKと同じである。
親水性オリゴマーO 7.00g、疎水性オリゴマーJ 4.47g、炭酸カリウム0.12g、DFB0.26g、NMP110mLを用い、実施例14と同様にして、スルホン酸基含有セグメント化ブロックポリマーPを得た(化59)。ポリマーPの対数粘度は、3.4dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Pを得た。ポリマーPの化学構造は親水性セグメントにもベンゾニトリルの構造をランダム構造で含むものである。
親水性オリゴマーP 7.00g、疎水性オリゴマーL 4.91g、炭酸カリウム0.10g、DFB0.26g、NMP110mLを用い、実施例14と同様にして、スルホン酸基含有セグメント化ブロックポリマーQを得た(化60)。ポリマーQの対数粘度は、2.5dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Qを得た。
合成例14と同様の仕込み比でNMPを317mlとなるように疎水性オリゴマーMを重合した。また、合成例17と同様の仕込み比でNMPを200mlとなるように親水性オリゴマーQを重合した。それぞれの重合溶液を混合し、1時間攪拌した。その後、DFB1.68gを加え、110℃に加熱し、10時間反応させた。精製は実施例14と同様にしてスルホン酸基含有セグメント化ブロックポリマーRを得た(化61)。ポリマーRの対数粘度は、3.5dL/gだった。得られたポリマーから上記の方法によってプロトン交換膜Rを得た。
合成例14と同様にして、DCBNの仕込み量を過剰にすることでCl末端を有する疎水性オリゴマーMを合成した。疎水性オリゴマーM 数平均分子量14200。仕込み量を変えた以外は合成例17と同様の方法でOH末端を有する親水性オリゴマーQを合成した。親水性オリゴマーQ 数平均分子量24110。であった。
用いるモノマーをDCBNから4,4‘-ジクロロジフェニルスルホン(DCDPS)にしたことと仕込みを変更した以外は合成例14と同様にして疎水性オリゴマーNを合成した(化64)。疎水性オリゴマーN 数平均分子量 13560であった。
デュポン社製20%ナフィオン(商品名)溶液に、市販の40%Pt触媒担持カーボン(田中貴金属工業株式会社 燃料電池用触媒 TEC10V40E)と、少量の超純水及びイソプロパノールを加えた後、均一になるまで撹拌し、触媒ペーストを調製した。この触媒ペーストを、東レ社製カーボンペーパーTGPH-060に白金の付着量が0.5mg/cm2になるように均一に塗布・乾燥して、電極触媒層付きガス拡散層を作製した。上記の電極触媒層付きガス拡散層の間に、高分子電解質膜を、電極触媒層が膜に接するように挟み、ホットプレス法により200℃、8MPaにて3分間加圧、加熱することにより、膜電極接合体とした。この接合体をElectrochem社製の評価用燃料電池セルFC25-02SPに組み込んでセル温度80℃で、アノード及びカソードにそれぞれ75℃で加湿した水素と空気を供給して発電特性を評価した。開始直後における電流密度が0.5A/cm2における出力電圧を初期出力とした。また、耐久性評価として、1時間に3回の割合で開回路電圧を測定しつつ上記の条件で2000時間を上限として連続運転を行った。開回路電圧が開始直後の値よりも10%以上低下したときの時間を耐久時間とした。実施例16のプロトン交換膜を用いたPEFC発電評価における初期電圧は0.73Vであり、連続運転では2000時間経過後も電圧低下は4%であり、耐久時間は2000時間以上であった。
比較例7のプロトン交換膜を用いて実施例22と同様にPEFC発電評価を行ったところ1670時間で出力が10%低下しており、耐久時間は1670時間であり、実施例22に比べ劣るものであった。
Claims (30)
- 分子中にそれぞれ一つ以上の親水性セグメントと疎水性セグメントを有するブロック共重合ポリマーであって、下記化学式1で表される構造であり、N-メチル-2-ピロリドンを溶媒とした0.5g/dLの溶液について30℃で測定される対数粘度が、0.5~5.0dL/gの範囲であることを特徴とするブロック共重合ポリマー。
(式中、XはH又は1価の陽イオンを、Yはスルホニル基、又はカルボニル基を、Z及びZ’はそれぞれ独立してO又はS原子のいずれかを、Wはベンゼン間同士の直接結合、スルホン基、カルボニル基からなる群より選ばれる1種以上の基を、Ar1及びAr2は、それぞれ独立して2価の芳香族基を、n及びmは独立して、それぞれ2~100の整数を、それぞれ表す。) - Ar1が上記化学式2で表される構造で表される構造であることを特徴とする請求項1に記載のスルホン酸基含有ブロック共重合ポリマー。
- Ar1及びAr2のいずれもが上記化学式2で表される構造で表される構造であることを特徴とする請求項1に記載のスルホン酸基含有ブロック共重合ポリマー。
- Z及びZ’の少なくともいずれかが、O原子であることを特徴とする請求項1~4に記載のスルホン酸基含有ブロック共重合ポリマー。
- Z及びZ’のいずれもがO原子であることを特徴とする請求項1~4に記載のスルホン酸基含有ブロック共重合ポリマー。
- Wがベンゼン環同士の直接結合であることを特徴とする請求項1~6に記載のスルホン酸基含有ブロック共重合ポリマー。
- nが10~70の範囲であることを特徴とする請求項1~7に記載のスルホン酸基含有セグメント化ブロック共重合ポリマー。
- mが3以上10未満の範囲であることを特徴とする請求項8に記載のスルホン酸基含有セグメント化ブロック共重合ポリマー。
- m/nが、0.4~1.0の範囲であることを特徴とする請求項9に記載のスルホン酸基含有セグメント化ブロック共重合ポリマー。
- mが10以上70未満の範囲であることを特徴とする請求項8に記載のスルホン酸基含有セグメント化ブロック共重合ポリマー。
- m/nが、0.4~1.5の範囲であることを特徴とする請求項11に記載のスルホン酸基含有セグメント化ブロック共重合ポリマー。
- 親水性オリゴマー、疎水性オリゴマーおよび分子中に少なくとも2つ以上のハロゲンを有する芳香族系鎖延長剤を反応させてブロック共重合体ポリマーを合成する方法において、疎水性オリゴマーが下記化学式7
(式中、Zはそれぞれ独立してO又はS原子のいずれかを、Ar1は2価の芳香族基を、nは2~100の整数を、それぞれ表す。)
で表される構造を分子中に含んでおり、親水性オリゴマーが下記化学式8
(式中、XはH又は1価の陽イオンを、Yはスルホニル基、又はカルボニル基を、ZはO又はS原子のいずれかを、Ar2は、2価の芳香族基を、mは2~100の整数を、それ
ぞれ表す。)
で表される構造を分子中に含むことを特徴とするブロック共重合ポリマーの合成法。 - 親水性オリゴマー及び疎水性オリゴマーの両末端がそれぞれOH基であることを特徴とする請求項13に記載のブロック共重合体ポリマーの合成法。
- 親水性オリゴマー及び疎水性オリゴマーの両末端がそれぞれSH基であることを特徴とする請求項13に記載のブロック共重合体ポリマーの合成法。
- 芳香族系鎖延長剤のハロゲンがフッ素であることを特徴とする請求項13~15に記載のブロック共重合体ポリマーの合成法。
- 芳香族系鎖延長剤がパーフルオロ化合物(ただし、シアノ基、スルホニル基、スルフィニル基、カルボニル基からなる群より選ばれる基を含んでいてもよい)であることを特徴とする請求項16に記載のブロック共重合体ポリマーの合成法。
- 芳香族系鎖延長剤がヘキサフルオロベンゼン、デカフルオロビフェニル、デカフルオロベンゾフェノン、デカフルオロジフェニルスルホン、ペンタフルオロベンゾニトリルのいずれか、またはこれらの混合物であることを特徴とする請求項17に記載のブロック共重合ポリマーの合成法。
- 反応溶液の固形分濃度が1~25重量%である反応溶液中で合成されることを特徴とする請求項13~18に記載のブロック共重合体ポリマーの合成法。
- 反応温度が50~160℃の範囲であることを特徴とする請求項13~19に記載のブロック共重合体の合成法。
- 少なくとも、(A)親水性オリゴマー溶液、(B)疎水性オリゴマー溶液、及び(C)分子中に少なくとも2つ以上のハロゲンを有する芳香族系鎖延長剤を必須成分として混合して反応させることを特徴とする請求項13~20に記載のブロック共重合体の合成法。
- 親水性オリゴマーの合成反応によって得られた反応溶液を親水性オリゴマー溶液として用い、かつ疎水性オリゴマーの合成反応によって得られた反応溶液を疎水性オリゴマー溶液として用いることを特徴とする請求項21に記載のブロック共重合体の合成法。
- 請求項1~12に記載のブロック共重合ポリマー、又は請求項13~22に記載の合成法で得られたブロック共重合ポリマーからなる成形物。
- 請求項1~12に記載のブロック共重合ポリマー、又は請求項13~22に記載の合成法で得られたブロック共重合ポリマーからなる燃料電池用プロトン交換膜。
- 請求項1~12に記載のブロック共重合ポリマー、又は請求項13~22に記載の合成法で得られたブロック共重合ポリマーを構成成分とするブロック共重合ポリマー組成物。
- 請求項25に記載のブロック共重合ポリマー組成物から得られる成形物。
- 請求項25に記載のブロック共重合ポリマー組成物から得られる燃料電池用プロトン交換膜。
- 繊維状物質を含むことを特徴とする請求項25に記載の燃料電池用プロトン交換膜。
- 請求項24、27、28のいずれかに記載の燃料電池用プロトン交換膜を用いた燃料電池用プロトン交換膜電極接合体。
- 請求項29に記載の燃料電池用プロトン交換膜電極接合体を用いた燃料電池。
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EP2289973A1 (en) | 2008-05-08 | 2011-03-02 | Toyo Boseki Kabushiki Kaisha | Novel sulfonic acid group-containing segmentalized block copolymer, use thereof, and method for producing novel block copolymer |
EP2414430A1 (de) | 2009-04-03 | 2012-02-08 | Basf Se | Verfahren zur herstellung von chlorarmen polybiphenylsulfon-polymeren |
EP2414430B1 (de) | 2009-04-03 | 2017-10-04 | Basf Se | Verfahren zur herstellung von chlorarmen polybiphenylsulfon-polymeren |
WO2011016444A1 (ja) * | 2009-08-03 | 2011-02-10 | 東洋紡績株式会社 | 新規スルホン酸基含有セグメント化ブロック共重合体ポリマー及びその用途 |
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JP2011181278A (ja) * | 2010-02-26 | 2011-09-15 | Kaneka Corp | 高分子電解質、その製法およびその用途 |
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WO2013027724A1 (ja) * | 2011-08-23 | 2013-02-28 | 東レ株式会社 | ブロック共重合体およびその製造方法、ならびにそれを用いた高分子電解質材料、高分子電解質成型体および固体高分子型燃料電池 |
KR20140051939A (ko) * | 2011-08-23 | 2014-05-02 | 도레이 카부시키가이샤 | 블록 공중합체 및 그의 제조 방법, 및 이를 사용한 고분자 전해질 재료, 고분자 전해질 성형체 및 고체 고분자형 연료 전지 |
JPWO2013027724A1 (ja) * | 2011-08-23 | 2015-03-19 | 東レ株式会社 | ブロック共重合体およびその製造方法、ならびにそれを用いた高分子電解質材料、高分子電解質成型体および固体高分子型燃料電池 |
KR101911982B1 (ko) * | 2011-08-23 | 2018-10-25 | 도레이 카부시키가이샤 | 블록 공중합체 및 그의 제조 방법, 및 이를 사용한 고분자 전해질 재료, 고분자 전해질 성형체 및 고체 고분자형 연료 전지 |
JP2016204670A (ja) * | 2011-08-23 | 2016-12-08 | 東レ株式会社 | ブロック共重合体およびその製造方法、ならびにそれを用いた高分子電解質材料、高分子電解質成型体および固体高分子型燃料電池 |
US9653745B2 (en) | 2011-08-23 | 2017-05-16 | Toray Industries, Inc. | Block copolymer, manufacturing method therefor, and polymer electrolyte material, molded polymer electrolyte, and solid-polymer fuel cell using said block copolymer |
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JPWO2015141653A1 (ja) * | 2014-03-19 | 2017-04-13 | 東洋紡株式会社 | 複合分離膜 |
WO2015141653A1 (ja) * | 2014-03-19 | 2015-09-24 | 東洋紡株式会社 | 複合分離膜 |
Also Published As
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JPWO2009136631A1 (ja) | 2011-09-08 |
US20110065021A1 (en) | 2011-03-17 |
EP2289973A4 (en) | 2011-07-06 |
JP5760312B2 (ja) | 2015-08-05 |
EP2289973B1 (en) | 2013-07-17 |
CN102015830A (zh) | 2011-04-13 |
CN102015830B (zh) | 2013-11-13 |
EP2289973A1 (en) | 2011-03-02 |
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